Skip to main content
NCBI home page
ACS Organic & Inorganic Au logoLink to ACS Organic & Inorganic Au
. 2022 Dec 30;3(2):74–91. doi: 10.1021/acsorginorgau.2c00056

Applications of Vanadium, Niobium, and Tantalum Complexes in Organic and Inorganic Synthesis

Xinru Xu †, Hong Wang †,*, Choon-Hong Tan ‡, Xinyi Ye †,*
PMCID: PMC10080730  PMID: 37035284

Abstract

graphic file with name gg2c00056_0033.jpg

Organometallic catalysis is a powerful strategy in chemical synthesis, especially with the cheap and low toxic metals based on green chemistry principle. Thus, the selection of the metal is particularly important to plan relevant and applicable processes. The group VB metals have been the subject of exciting and significant advances in both organic and inorganic synthesis. In this Review, we have summarized some reports from recent decades, which are about the development of group VB metals utilized in various types of reactions, such as oxidation, reduction, alkylation, dealkylation, polymerization, aromatization, protein synthesis, and practical water splitting.

Keywords: group VB metal, vanadium, niobium, tantalum, organometallic catalysis, asymmetric synthesis, green chemistry, inorganic synthesis

1. Introduction

Catalysis plays an important role in both laboratory and industry because it can enhance the efficiency and is environmentally benign. For more reasons, the development of catalysts is important in industry, such as for its cost, hazards, and recycling capability. The selection of the metal is particularly important to plan relevant and applicable processes. Transition metals are very important catalysts in organic synthesis, so it is of great value to find suitable options. In the past decade, metal catalysis technology has been widely developed and has achieved great success.1−13 Due to the unique advantages of transition metals in organic catalytic reactions, metal catalysis has been developed vigorously in recent years. Metal-catalyzed organic reactions have attracted the attention of many organic chemists, because the results of transformative reaction processes continuously produce chemicals used in daily life, especially cheap metals like nickel,5−7 copper,8,9 iron,10,11 and cobalt.12,13 Therefore, it is important to use abundant and relatively biocompatible metals, such as vanadium.

Due to the diversity of anionic and neutral ligands that can form stable complexes with group VB elements, there is considerable literature on the application of group VB elements in organic and inorganic synthesis.14−17 The application of group VB metal complexes as catalysts in organic and inorganic reactions maintains a high profile.

Vanadium is an ideal option because it is cheap, naturally abundant and relatively nontoxic. In nature, vanadium is rarely existing as elemantary substance, but separately and mainly forms symbiotic ore or compound ore with other minerals. Moreover, it is widely used in many fields due to its rich redox chemistry.18 The main forms of vanadium in practical examples include vanadium pentoxide, vanadium trioxide, vanadium iron, vanadium nitride, and so on. Vanadium plays an important role in biochemistry19−22 and medicinal chemistry,23−25 and its variety in coordination chemistry led to applications in synthesis and catalysis.26−36 Niobium and tantalum are very similar in physical and chemical properties, and they usually exist together in nature. In fact, niobium and tantalum were thought to be one element when they were discovered in the early 19th century. Compared with vanadium, niobium and tantalum are less studied. Niobium is a multifunctional element, which can be used in catalysts.37,38 Tantalum is mainly found in tantalite, niobite, and coltan, and is relatively rare compared to other metals. The application of tantalum compounds in catalytic reactions has also attracted significant attention. Several recent reviews clearly illustrate advances and achievements of group VB element chemistry in different fields.39−48

This Review specifically focuses on recent advances in the progress of utilizing vanadium, niobium, and tantalum in various organic and inorganic synthesis, including oxidation, reduction, water splitting, alkylation, dealkylation, polymerization, aromatization, protein synthesis, and so on (Figure 1). Compounds with high valence states of Nb/Ta were often required for the catalysis of oxidation and water splitting. Oxidation and water splitting always needed pentavalent V/Nb or V(IV) complexes with pro-oxygenic agent. As for reduction, the low-valent niobium complexes acted as real active catalysts and were in situ generated from pentavalent Nb/Ta and another reductive metal such as Zn. Pentavalent V/Nb/Ta complexes were needed as catalysts for polymerization and protein synthesis in most cases. Dealkylation and alkylation usually used pentavalent metal complexes, whereas in a few cases, the metals were in the trivalent state. In addition, both Ta(III) or Nb(III/V) could be used as catalysts for aromatization. In this Review, some representative works are illustrated, and mechanistic studies are revealed in detail based on developments in recent decades.

Figure 1.

Figure 1

Open in a new tab

Broad applications in organic and inorganic synthesis of group VB elements.

2. Organic Synthesis

2.1. Oxidation

Vanadium has multiple valence states, with oxidation states ranging from bivalent to pentavalent as reductants to strong oxidants. Among these, the charge of plus five is the most stable state, followed by vanadium plus of four. Vanadium compounds can be used for epoxidation, dehydrogenation, and sulfoxidation. Niobium and tantalum have very similar chemical properties due to the same outermost electrons. The most stable valence state of niobium tantalum is also plus five. In general, niobium is more easily reduced than tantalum. Thus, they are commonly used as photocatalysts for oxidation.49 The representative structures of V, Nb, and Ta are shown in Figure 2. Especially, vanadium oxide complexes were the most practical options and utilized as catalysts for olefin epoxidation and sulfoxidation in the presense of O2 or peroxide reagents as terminal oxidants.50

Figure 2.

Figure 2

Open in a new tab

Common structure of oxo and alkoxo complexes of V, Nb, and Ta.

2.1.1. V, Nb-Catalyzed Epoxidation

Chiral epoxides are fundamental building blocks in natural products and biologically active compounds. As early as 1973, Sharpless and colleagues reported a promising asymmetric catalyst for vanadium complex.51−54 VO(acac)2 was combined with chiral hydroxamic acid 1, and the optically active epoxides were synthesized from allyl alcohol with tert-butyl peroxide (TBHP) or other oxidants. The enantioselectivity of the product was up to 50% (Scheme 1a).51 Although the enantioselectivity of asymmetric epoxidation catalyzed by the vanadium complex was not perfect, it was considered a major success accounting for the direct strategy of synthesizing high-value chiral epoxides from readily available allyl alcohols.

Scheme 1. Early Exploration of Synthesizing Racemic and Chiral Epoxides.

Scheme 1

Open in a new tab

In the next two decades, the epoxidation of allyl alcohol catalyzed by vanadium was still in its infancy. However, Yamamoto and colleagues reported a giant improvement in 1999, obtaining epoxide with up to 94% ee (Scheme 1b).55,56 Hydroxamic acid 2 was proved to be the most efficient axially chiral ligand. In order to improve the efficiency of vanadium catalyst, efforts should be made in many aspects such as chiral source, catalyst ligand, and reaction conditions. Based on previous studies, Yamamoto introduced a new amino acid, hydroxamic acid, ligand. Its applicability in catalytic oxidation was demonstrated.57,58 In these case, Hoshino and Yamamoto found that, in vanadium-catalyzed epoxidation, hydroxamic acid 3 (Scheme 1b) was the most efficient ligand to pursue enantioselectivities (up to 96% ee).57 The chiral vanadium catalyst can be used for asymmetric epoxidation under mild conditions with good chemoselectivity and enantioselectivity (58–89% yield, 84–91% ee).

Since hydroxamic acid ligands had been shown to be effective, the rate and enantioselectivity of the reactions were significantly enhanced. However, the ligand deceleration effect was still pending ideal solutions.55−57 To eliminate this effect, Yamamoto et al. designed a novel C2-symmetric bishydroxamic acid 4 that preserved the high reactivity and selectivity (>90% ee) of the vanadium-ligand complex (Scheme 2a). The influence of dynamic ligand exchange was successfully avoided in this catalytic system.59 Subsequently, the catalytic system was used for kinetic resolution of allyl alcohol, and satisfactory enantiopurity was obtained for both reactants and products (>90% ee) (Scheme 2b).60 Due to the inherent problems, kinetic resolution is not the best strategy to prepare optically pure epoxides from homoallylic alcohols. Therefore, Yamamoto and co-workers tried to apply the catalytic system to the desymmetrization reaction and obtained satisfactory results with up to 97% ee (Scheme 2c).61

Scheme 2. Vanadium Complex Catalyzed Enantioselective Epoxidation with C2-Symmetric Bishydroxamic Acid Scaffold.

Scheme 2

Open in a new tab

Florfenicol 7 is a synthetic monofluoride derivative of thiamphenicol 8 (Scheme 3). It has been widely used for its great advantages in antibacterial spectrum. On the basis of the above catalytic system, Chen et al. designed the proposal using the asymmetric vanadium catalyzed epoxidation as the key step in total synthesis of florfenicol 7 (Scheme 3).62

Scheme 3. Asymmetric Epoxidation with Yamamoto’s Vanadium Catalyst.

Scheme 3

Open in a new tab

Malkov et al. proposed epoxidation in water using a complex of VOSO4 and hydroxamic acid ligand 9 as an active catalyst to obtain a series of epoxides (up to 94% ee) (Scheme 4a). Through this strategy, the common ligand deceleration effect was effectively avoided; furthermore, the reaction was found to be a ligand acceleration process.63

Scheme 4. Asymmetric Epoxidation by V/Nb/Ti Catalysts with Other Chiral Ligands.

Scheme 4

Open in a new tab

Axially chiral C2-symmetric binaphthyl derivatives have been widely used as chiral ligands in many enantioselective reactions.64,65 In 2015, asymmetric epoxidation catalyzed by vanadium complex with binaphthylbishydroxamic acid (BBHA) 10 was reported by Noji and co-workers.66 By this method, multisubstituted epoxides were obtained in excellent enantioselectivities (Scheme 4b).

Katsuki et al. reported an asymmetric epoxidation of allylic alcohols catalyzed by Nb-salan complexes for the first time in 2010.67 As a result, highly enantio-enriched epoxides (up to 95% ee) were obtained by using catalyst 11 (Scheme 4c). In fact, compounds resulting from the combination of salan ligands with a variety of metals such as titanium or manganese are used as catalysts. Previously, Ti-salan complex 12 was reported as a highly efficient catalyst for epoxidation.68

Takizawa, Sasai et al. demonstrated a vanadium(V) complex catalyzed oxidative coupling of polycyclic phenols to synthesize chiral oxa[9]helicenes (Scheme 5).69 The complex promoted reactions as both redox and Lewis acid catalysts, providing a good yield of products with high enantioselectivity (up to 94% ee). Chiral vanadium complex 15 was proved to be the most active catalyst.69

Scheme 5. V-Catalyzed Oxidative Coupling of Polycyclic Phenols.

Scheme 5

Open in a new tab

2.1.2. V-Catalyzed Sulfoxidation

Chiral sulfoxides have a rich history in asymmetric synthesis,70−72 and one of the useful applications in enantioselective catalysis is they work as ligands.73−75 Sulfide oxidations catalyzed by V, Nb complexes were also concerned, and catalytic mechanisms had been studied.76−78 V/Nb-catalyzed sulfur oxidations were chemo- and stereoselective, resulting in sulfoxides with high enantioselectivities.

In 1986 and 1990, Fujita and Nakajima et al. reported an asymmetric sulfur oxidation catalyzed by optically active Schiff base oxovanadium(IV) compounds.79,80 The optimal enantioselectivities of products were between 20 and 40% ee. When methyl phenyl sulfide was oxidized to sulfoxide using complex 16 (Scheme 6a) as catalyst and cumyl hydroperoxide (CHP) as oxidant (Scheme 6), the enantioselectivity was up to 42%. In 1989, oxovanadium(V) complex 17 (Scheme 6a) was synthesized with an amino acid-derived Schiff base as ligand which gave optically active sulfoxide with t-butylhydroperoxide (TBHP) as oxidant. However, the highest enantioselectivity of the product was only 14% ee.81

Scheme 6. V-Catalyzed Enantioselective Sulfur Oxidation.

Scheme 6

Open in a new tab

Based on previous studies, in 1995, Bolm and Bienewald introduced the oxidation catalysts 18 (Scheme 6a) formed in situ from Schiff base and vanadyl acetylacetonate. Using this catalytic system, less than 1 mol % catalyst was enough to produce sulfoxides with up to 85% ee.82 It was found in 1996 that vanadium(IV) complex 19 (Scheme 6a) with oxazolinylphenol as ligand could catalyze asymmetric sulfur oxidations. But this time the catalyst was highly active to initiate the reaction, and the resulting product was racemized.83

Wang and Sun et al. used Schiff bases 20 or 21 (Scheme 6b) in association with VO(acac)284 as catalysts. By this way, the asymmetric sulfoxides oxidized by H2O2 were obtained in 48–62% yields with relatively high enantioselectivities (91–94% ee), which were significantly higher than the catalytic results obtained from the same reaction with Schiff base 18 (Scheme 6a) as ligand. Tsogoeva et al. used ligand 22 or 23 (Scheme 6b) with VO(acac)2 as catalyst,85 but the enantioselectivity of the product was only up to 45% ee.

In 2013, Singh et al. synthesized a recylclable heterogeneous VIVO-Sal-Indanol complex 24 (Scheme 6c) over SBA-15 for enantioselective sulfoxidation.86 This kind of synthetic catalyst showed high activity but moderate enantioselectivities (30–33% ee). Rostami et al. designed the chiral oxo-vanadium (+)-pseudoephedrine complex 25 (Scheme 6c) supported on magnetic nanoparticles Fe3O4, which utilized H2O2 to catalyze the oxidation of sulfides with high chemoselectivity.87 This kind of heterogenized catalyst can be easily recovered with suitable external magnets. However, sulfoxides were obtained with only 20–27% ee.

Ward et al. selected VOSO4 as vanadyl source in conjunction with streptavidin to constitute an artificial enzyme for sulfoxidation of prochiral substrates for sulfoxidation.88 After determining the optimal reaction condition, products with satisfactory enantioselectivity (up to 93% ee) could be obtained with moderate to high conversions.

A novel new enantiopure oxido-vanadium supramolecular catalyst89 for selective oxidation of sulfides was introduced by Martinez and colleagues. The new catalyst showed excellent catalytic ability, and its turnover number (TON) was nearly 105. The complex has a bowl-shaped structure with a hydrophobic pocket above it, which is beneficial to improve the enantioselectivity of the reaction. Compared with other vanadium catalysts (such as Schiff base complexes), although the enantioselectivity of the products was lower, this kind of C3-symmetric vanadium complex has unique asymmetric catalytic effects. Shen et al. introduced a novel silica supported chitosan vanadium complex, which was described as an active heterogeneous catalyst for asymmetric sulfur oxidation.90 Using H2O2 as oxidant, the products were obtained in up to 95% yield with up to 68% ee. This strategy was applied to the preparation of the proton pump inhibitor Esomeprazole.

2.1.3. V-Catalyzed Oxidative Coupling

In addition to above, oxidation also includes oxidative coupling. The optically active 1,1′-bis-2-naphthol (BINOL) and its derivatives are widely used as ligands in various asymmetric transformations and catalytic reactions in the presence of suitable Lewis acids.91−93

A series of chiral vanadium oxide complexes have served as effective catalysts for enantioselective oxidative coupling of various phenols.94,95 Most of them showed good perfomance in enantioselectivity. According to Uang et al.,96 chiral BINOLs were obtained by enantioselective oxidative coupling of 2- naphthol with chiral vanadium oxide complex 26 (Scheme 7) under mild conditions, showing moderate enantioselectivity (up to 50% ee). Chen and co-workers used the vanadium complexes 27 (Scheme 7) in CCl4 for the enantioselective oxidative couplings, producing BINOLs with good to excellent yields (75–100%) and enantioselectivities (up to 68% ee).97 After this, oxovanadium(IV) complexe 28 was synthesized (Scheme 7) for oxidative couplings of various substituted 2-naphthols leading to products in 61–99% yields and up to 87% ee.98 Besides, Gong et al. designed a series of oxovanadium(IV) complexes 29 (Scheme 7) for similar reaction with the same reaction conditions, and ideal enantioselectivities of products was achieved (83–98% ee).99

Scheme 7. Chiral BINOL Synthesis via Vanadium Complexes with Chiral Schiff Bases.

Scheme 7

Open in a new tab

Sasai et al. prepared chiral mononuclear and dinuclear vanadium(V) catalysts with high activity for the oxidative coupling of substituted 2-naphthols. With dinuclear vanadium(V) complex 30 (Scheme 8) as catalyst, (S)-BINOLs were obtained in excellent enantioselectivities (up to 97% ee).100 In 2017, Takizawa, Oh et al. described a controllable enantiodivergent approach to synthesize chiral BINOLs via asymmetric dehydrogenation coupling. By using mononuclear or dinuclear vanadium(V) catalysts, modified 2-naphthols were homocoupled in reversed configurations.101 With dinuclear vanadium catalyst 30 (Scheme 8), the reaction was achieved by intramolecular coupling, while with mononuclear catalyst 31 (Scheme 8), the reaction was achieved by intermolecular coupling. In the next year, Takizawa et al. succeeded in dehydrogenation coupling of hydroxycarbazoles with up to 80% ee using chiral dinuclear vanadium complexes.102

Scheme 8. Other Enantioselective Homo- and Cross Coupling between Arenols via Chiral Vanadium Catalysts.

Scheme 8

Open in a new tab

Soon afterward, oxidative coupling under air was proposed using substituted resorcinols as substrates (Scheme 8a). High regio- and enantioselective biresorcinols were obtained using dibrominated binuclear vanadium(V) catalyst 32 (Scheme 8).103

Subsequently, the catalysts were applied to oxidative heterocoupling of arenols (Scheme 8b). Hydroxyl carbazole derivatives and various arenols acted as substrates reacting under mild conditions catalyzed by 33 (Scheme 8).104 The products were obtained with high yield and up to 90% ee.

In 2017, Kozlowski et al. also reported asymmetric oxidative coupling catalyzed by vanadium(V) catalyst. They were the first choosing simple phenols or 2-hydroxycarbazole as substrates. Using vanadium catalysts 34, products were obtained with up to 96% ee (Scheme 9).105 Catalyst 34 showed low reactivity and selectivity because of the weak Lewis acidity. However, it was found that an exogenous Brønsted or Lewis acid could improve the acidity and stabilize the catalyst. By this way, an in situ acidic oxidative catalyst was developed with stronger oxidative capacity. In addition, a homocoupling of benzoheteroarenols was realized via 34.

Scheme 9. Influence of Acidity in Oxidative Coupling.

Scheme 9

Open in a new tab

2.1.4. V,Nb-Catalyzed Photooxidation

V/Nb complexes have excellent catalytic capacity for photocatalytic conversion of various organic compounds.106,107 BiVO4, a visible-light-responsive photocatalyst, has shown activity in photocatalytic108 and photoelectrochemical water oxidation.109 Liu, Li, and co-workers proposed using BiVO4 as an efficient photocatalyst for the aerobic oxidation of amines under mild conditions (Scheme 10a), and a series of imines were obtained with high selectivity (up to 99%).110

Scheme 10. Photocatalytic Oxidation of Amines.

Scheme 10

Open in a new tab

Niobium pentoxide (Nb2O5), a nontoxic metal oxide, is ecofriendly and shows strong oxidation ability. Shishido and Tanaka et al. found that Nb2O5 showed high catalytic activities. It catalyzed the oxidation of alcohols under irradiation, producing carbonyl compounds with good selectivity.107

In 2011, it was found that Nb2O5 could act as a highly efficient photocatalyst for selective oxidation of benzylamine (Scheme 10b).111 Various amines were converted to imines in excellent yields (95–99% yield) and high selectivity by using Nb2O5.

Soon after, the mechanism of photocatalytic oxidation of amine catalyzed by Nb2O5 was studied in detail.112 FT-IR spectra, ESR measurements and DFT calculations showed that substrate amines were first adsorbed on Nb2O5 (Step i, Scheme 10), and then the complex was photoactivated (Step ii, Scheme 10). Subsequently, the α–C-H bond was activated to obtain imines (Step iii, Scheme 10).

After exploration, it was also found that Nb2O5 showed catalytic activity and selectivity to partial oxidation products. Photooxidation of alcohols catalyzed by Nb2O5 mainly led to aldehydes, while aerobic photooxidation of hydrocarbons mainly led to ketones without solvent.113 Soon afterward, Shishido, Tanaka, and co-workers prepared some catalysts, especially TiO2 covered by Nb2O5. It was found that Nb2O5/TiO2 system showed better photocatalytic activity than Nb2O5 in ethanol photooxidation.114 Through ESR study, they found that the catalytic system could effectively inhibit the generation of O3, which was known by its high activity and capacity of oxidizing compounds completely. In 2014, they found that Nb2O5 could also be used for selective oxidation of primary alcohols to produce aldehydes.115 The reaction mechanism is similar to oxidation of amines (Scheme 10).

In 2016, Hosokawa and Tanaka et al. synthesized Nb2O5 composed of nanoplate particles and demonstrated their photocatalytic activity.116 The photocatalytic activity of the niobium material was related to the surface property. With a large surface area, Nb2O5 showed high catalytic activity, and as a result, benzyl alcohol could be selectively oxidized to benzaldehyde (Scheme 11a).

Scheme 11. Selective Photooxidation of Benzyl Alcohol.

Scheme 11

Open in a new tab

In 2017, it was proposed photocatalytic aerobic oxidation of arene could be catalyzed by Nb2O5 under visible light irradiation via ligand-to-metal charge transfer (LMCT) transition.117 This process underwent a similar mechanism. First, toluene adsorbed on Nb2O5, and subsequently free radical cations were produced under light irradiation. Benzyl peroxy radicals were produced in the presence of oxygen, and finally, the radicals decomposed into benzaldehyde.

Amarante et al. prepared novel supported Nb2O5 catalysts which were used to selectively convert anilines to azoxybenzenes.118 Under the optimal standard conditions, a mass of substituted anilines were well tolerated, providing azobenzene with up to 92% yield (Scheme 11b). This is the first time using niobium supported on mixed metal oxides as photocatalysts for anilines oxidation. The dual role of catalysts was also revealed working as either Lewis acids or photocatalysts in the reaction. During the photocatalytic pathway, the key intermediate was nitrosobenzene.

2.1.5. Nb-Catalyzed Dehydration

Chung et al. tested the catalytic effects of various metal chlorides for fructose dehydration to 5-hydroxymethylfurfural (HMF) in ionic liquids (Scheme 12a).119 Of all the metals tested, niobium pentachloride exhibited the highest activation. According to FTIR analysis, they suspected that this may be because of its moderate Lewis acidity.

Scheme 12. Nb-Catalyzed Dehydration and Mechanism.

Scheme 12

Open in a new tab

Wu, Wu et al. used Nb2O5 to catalyze the oxidation of HMF.120 By this way, 2,5-diformylfuran was obtained selectively. It was determined that the reaction followed a different mechanism. First, the alcoholic hydroxyl group of HMF chelated on Nb2O5, then the comlexe formed and was activated under visible light (Scheme 12b). Furthermore, Kong, Lei, and co-workers constructed bifunctional ZnIn2S4/Nb2O5 photocatalysts which also showed catalytic capacity for the oxidation of HMF.121 The most remarkable advantage of the novel catalyst was that both photocatalytic reduction of H2 and oxidation of HMF could be carried out simultaneously.

2.1.6. V-Catalyzed Oxidative C–C or C–O Bond Cleavage

Oxidative C–C bond and C–O bond cleavage is a fundamental method to obtain aldehydes and ketones. Licini et al. reported aerobic oxidative C–C bond cleavage of glycols (Scheme 13a).122 V(V) amino triphenolate complex 35 was proved to be efficient catalysts for this reaction obtaining carbonyl derivatives with high yields and good selectivity. Moreover, catalyst loadings of the catalyst was down to 0.001%, and TONs of the catalyst was up to 81,000.

Scheme 13. V-Catalyzed C–C and C–O Bond Cleavage.

Scheme 13

Open in a new tab

Vanadium oxide has many important applications in a variety of oxidation reactions. Solid oxide catalysts were easy to isolate for the purpose of recycling.123 Wachs and co-workers studied V-based heterogeneous catalyst (supported VO4/SiO2).124,125 They discussed the reactivity difference of methanol oxidation catalyzed by aqueous bioinorganic enzyme mimics 36 and heterogeneous solid vanadium oxide catalyst 37 (Scheme 13). It was proposed that the difference was related to the activation energy for the C–H bond cleavage of the V–OCH3.125 Besides, Strunk et al. investigated the effects of supported vanadium oxide species and degree of oligomerization on photocatalytic methanol oxidation.126

Fang and co-workers reported a Cu–V bimetallic catalyst (CuVOx) catalyzed heterogeneous Fenton process for the degradation of fluconazole.127 It was found that this novel catalyst had higher catalytic activity and better reusability than those of monometallic Cu compounds. The CuVOx Fenton system showed hopeful prospects in the degradation of various organic pollutants. Licini, Kleij, and co-workers demonstrated that V(V) amino triphenolate complexes were highly active catalysts for the coupling of epoxides and CO2 (Scheme 13b).128 V(V) complex 37 and ammonium salts formed binary catalysts and could catalyze the generally challenging conversion of epoxides and CO2.

In recent years, degradation of lignocellulosic biomass has attracted great attention for the potential of exploiting it as a chemical fuel. And it was found the vanadium catalyst could contribute to lignin degradation. Toste and Son proposed that changing the catalyst ligand could yield different main products (Scheme 14).129 It made the reaction controllable in high chemoselectivity. It was a novel approach to selectively obtain C–O bond cleavage products rather than benzylic alcohol oxidation products.

Scheme 14. Degradation of Lignin through C–O Bond Cleavage.

Scheme 14

Open in a new tab

Many studies have been carried out on selective lignin cleavage by Hanson and co-workers.130−133 A new approach of reaction mediated by V-catalyst 39 was reported in 2012. The C–C bond was broken, obtaining acrolein derivative, 2,6-dimethoxybenzoquinone, and ketone (Scheme 15). Subsequently, different lignin model compounds were investigated including β-1 lignin model compounds132 and 2-phenoxyethanol lignin model compounds.133 According to above experiments, they speculated a diverse degradation pattern dominated by catalysts. In 2016, Fu et al. clarified the mechanism of the diverse degradation system.134

Scheme 15. Degradation of Lignin through C–C Bond Cleavage.

Scheme 15

Open in a new tab

Corma, Bolm, and co-workers used hydrotalcites (HTc) and V(acac)3/Cu(NO3)2·3H2O mixtures as catalyst for oxidative cleavage of lignin.135 The catalytic system showed high reaction activity and selectivity and afforded acid as the main product (Scheme 16).

Scheme 16. Cu–V-catalyzed Degradation of Lignin.

Scheme 16

Open in a new tab

Besides, Wang et al. tested the selectivity of vanadium catalysts for lignin cleavage under visible light irradiation.136 Aldehydes can be obtained selectively by tuning the conditions and catalysts. It was proposed that visible light initiated a single electron transfer between substrate and catalyst, further inducing selective cleavage of the Cα–Cβ bond. Finally, products were obtained through the radical intermediates.

2.2. Deoxygenation (Reduction)

Low-valent niobium was reported used in some reductions. In 1990, Takai, Oshima, Utimoto et al. rechecked their previous catalysts using a reductant without hydride source.137 Quenched by NaOD-D2O, the combination of NbCl5 and zinc was found to give adjacent dideuterated (Z)-olefins as products with 52–86% yield. In this process, low-valent group VB metals formed complexes with alkyne. In 1992, various tantalum-alkyne complexes and niobium-alkyne complexes were generated.138 The reaction with carbonyl compounds catalyzed by these two complexes obtained different products, which was due to the different reaction processes (Figure 3). The tantalum catalyzed reaction yielded (E)-allylic alcohols in high stereoselectively, while niobium catalyzed reduction formed 1,3-diene. They believed that the strong oxygen affinity of niobium was conducive to deoxidation elimination.

Figure 3.

Figure 3

Open in a new tab

Working models of reduction with carbonyl compounds.

More examples of reductions, such as deoxygenation of epoxides, sulfoxides, and amine N-oxides, were reported by Oh and co-workers. They used the low-valent niobium complexes that was in situ generated from NbCl5 and Zn (Scheme 17a).139 Liang and Wu et al. developed a Nb4+ assisted strategy to produce in situ growth of highly dispersed Pd nanoparticles on monolayer HNb3O8 nanosheets without extra reductant and stabilizer.140 Photoactive HNb3O8 nanosheets and loaded Pd nanoparticles played a synergistic role under light irradiation, which improved the catalytic reduction efficiency of nitro compounds (Scheme 17b).

Scheme 17. Nb-Catalyzed Reduction.

Scheme 17

Open in a new tab

In 2019, Ribeiro et al. firstly reported acidic surface Nb2O5 catalysts with remarkable activity for CO2 reduction.141 This process undergoes physisorption of CO2 and photocatalysts and then activation by ultraviolet radiation to induce reduction and oxidation. And according to Sun and Xie et al., waste plastics were converted into C2 fuel with high selectivity using Nb2O5 as catalyst through photoinduced C–C cleavage and coupling under conditions close to those in nature.142

2.3. Dealkylation and Alkylation

The group VB elements can also serve as catalysts for dealkylation and alkylation. Arai, Nishida and co-workers described a method for the cleavage of C–O bonds catalyzed by niobium(V) pentachloride (Scheme 18).143 The phenols were obtained with excellent yields and regioselectivities and in this system, Nb(V) also acted as a Lewis acid. SN1 substitution occurred during ether bond cleavage process.

Scheme 18. Dealkylation of Derived BINOL.

Scheme 18

Open in a new tab

As early as 1987, it was proposed by Pedersen et al. that such metals could be used as catalysts for the Mannich reaction. Nb(III) reagent NbCl3(DME) was first synthesized to catalyze the preparation of 2-amino alcohols (Scheme 19a) with up to 90% yield conveniently.144 NbCl3(DME) was generated from a solution of NbCl5 and Bu3SnH in dimethoxyethane.

Scheme 19. Synthesis of 2-Amino Alcohols and α-Amino Amides via Alkylation Catalyzed by Nb/Ta.

Scheme 19

Open in a new tab

In 2005, Kobayashi et al. developed a method for the preparation of α-amino amides. They chose imines and isocyanates as substrates and low-valent tantalum prepared in situ from zinc and TaCl5 as catalysts.145 This method can be applied to a wide range of substrates and products were obtained with high yields (Scheme 19b).

Beside the C–N bond formation in hydroamination, hydroaminoalkylation is another powerful method for catalytic alkene amination by forming a C–C bond. Maspero and Clerici146 and Nugent et al.147 initially reported the hydroaminoalkylation using Nb/Ta as catalysts.

In 2007, Hartwig and Herzon described a tantalum-catalyzed hydroaminoalkylation for olefin amination. In this approach the α–C-H bonds of amines was added to the olefin, resulting in branched alkylamines (Scheme 20a).148 This reaction specifically functionalized saturated alkyl over aromatic C–H bonds with high selectivity. However, the reaction required comparatively high temperature and an aryl substituent on nitrogen. It was proposed that an η2-imine complex would be generated to serve as an electron-withdrawing group, avoiding the stable chelation between substrate and metal.

Scheme 20. Hydroaminoalkylation Catalyzed by Ta Complexes.

Scheme 20

Open in a new tab

Later, the catalytic system was enhanced to get rid of the limitation in substrate scope (Scheme 20b). Tantalum chloroamido complexes catalyzed the hydroaminoalkylation of olefins with unprecedented efficiency.149 In this process, the η2-imine complex was generated by the elimination of amine, and then the olefin inserted into the complex. Finally, products were obtained with the protonation (Scheme 20).

Hultzsch et al. discovered that BINOL-based niobium and tantalum complexes as catalysts could promote asymmetric hydroaminoalkylation, which achieved enantioselectivities up to 80% ee (Scheme 21a).150 These catalysts can also catalyze the hydroamination or cyclization with up to 81% ee. After intensive research, the role of catalysts in intermolecular hydroaminoalkylation was reported in 2012 and products were obtained with up to 98% ee (Scheme 21b).151

Scheme 21. Hydroaminoalkylation Catalyzed by Ta or Nb Complex.

Scheme 21

Open in a new tab

Schafer and co-workers extensively studied hydroaminoalkylation catalyzed by metal tantalum and niobium.152−159 They developed a series of different tantalum or niobium complexes as catalysts. And this catalytic system was proved to have excellent activity. Different ligands were designed to combine with tantalum and niobium. In this way, the activity and selectivity of the catalytic system could be adjusted.

In 2013, it was first realized that hydroaminoalkylation reactions could be achieved at room temperature catalyzed by phosphoramidate complex 41 (Scheme 22a).157

Scheme 22. Hydroaminoalkylation Catalyzed by Ta Complexes According to Schafer.

Scheme 22

Open in a new tab

In the last few years, Schafer and co-workers continued studied the application of tantalum based catalysts in the hydroaminoalkylation. In 2020, N,O-chelated cyclic ureate tantalum complex 42 was first synthesized (Scheme 22b) and showed higher activity.160 This system is suitable for both aryl and alkyl amine substrates. Generally speaking, hydroaminoalkylation of alkyl secondary amines is considered to be more challenging, but the catalytic activity of alkyl secondary amines was higher.

In 2021, in situ generated Ta-catalyst was reported for the alkylation of various unprotected N-heterocycles (Scheme 22c).161 In this catalytic system, most cases tended to produce branched chain products. However, by changing the electrical properties of the olefin, products with linear structures can be obtained as well. After this work, the effects of N,N-chelating guanidinate ligands were also tested.162

In group VB elements, Ta(V) catalysts were studied the most in hydroaminoalkylation. The group VB metal catalysts mainly focused on ligand design.163−165 Hydroaminoalkylation catalyzed by group 5 metals showed excellent regioselectivity and mainly obtained the branched product.

2.4. Miscellaneous

2.4.1. Aromatization

Aromatization is a practical method to construct aromatic rings, which benefits the petrochemical industry by integrating petrol pyrolysis. Metal-catalyzed aromatization has also been greatly developed, and many metals have been proven to have good catalytic effects such as Rh,166 Ru,167 Fe,168 Pd,169 Co,170 Mn,171 Cu,172 and so on.

In 1989, Pedersen et al. reported a regioselective synthesis of 2,3-disubstituted-1-naphthols (Scheme 23a) and pyrroles (Scheme 23b) promoted by NbCl3(DME).173,174 With this catalytic system, naphthols and pyrroles were obtained with high selectivity and good yield.

Scheme 23. Aromatization Catalyzed by NbCl3(DME).

Scheme 23

Open in a new tab

Takai, Utimoto, and co-workers prepared substituted 1-naphthols regioselectively catalyzed by the tantalum- and niobium-alkyne complexes with up to 93% yield.175 Du Plessis et al. used NbCl5 to catalyze the co-cyclotrimerization of hexyne and phenylacetylene.176 It was proposed that the reaction yields a cyclopentadiene intermediate formed by the combination of two acetylene molecules and the catalyst. In 1995, Takai, Utimoto, and co-workers reported the cyclotrimerization of alkyne catalyzed by tantalum-alkyne complexes.177 In 2004, Oshiki and Takai et al. characterized tantalum-η2-alkyne complexes exhibiting high catalytic activity for alkyne cyclotrimerization.178

Obora, Ishii, and co-workers reported the intermolecular [2 + 2 + 2] cycloaddition of alkenes to give 1,3-cyclohexadienes catalyzed by low-valent niobium: NbCl3(DME) (Scheme 24a),179−181 NbCl5/(TMS)3SiH (Scheme 24b),182 and NbCl5 (Scheme 24c).183,184 It was shown that low-valent niobium has excellent catalytic activity. Comparing NbCl3(DME) with NbCl5, the catalytic system with NbV showed higher chemo- and regioselectivity.

Scheme 24. Intermolecular Cycloaddition of Alkenes Catalyzed by Niobium Complexes.

Scheme 24

Open in a new tab

In 2012, a simple strategy for the synthesis of substituted pyrimidine derivatives catalyzed by NbCl5 was reported. The intermolecular cycloaddition reactions of an acetylene and two nitrile molecules were with good chemical and regionally selectivity (Scheme 25a).185 By using NbCl5 as catalyst, the target products, trisubstituted pyridine derivatives, could not be obtained. Thus, Obora and Satoh designed another high activity catalytic system, the NbCl5/Zn/alkoxysilane system for cycloaddition of alkynes with nitrile (Scheme 25b).186 The Nb(OEt)5/Grignard reagent system could catalyze isocyanate cyclotrimerization (Scheme 25c).187 And compared with applying only NbCl5, it was found that the use of Grignard reagent could improve the catalytic activity.

Scheme 25. Intermolecular Cycloaddition of Alkenes Catalyzed by Niobium Complexes.

Scheme 25

Open in a new tab

In 2017, low-valent Nb compounds were proposed for the synthesis of bicyclic cyclohexadienes. Products were obtained in high yields and high chemoselectivities between diynes and simple alkenes.188 The low-valent Nb compounds were obtained by a NbCl5/Zn/PCy3 catalytic system. At almost the same time, a FeCl3-assisted niobium-catalyzed [2 + 2+2] cycloaddition was developed to obtain pyrimidine derivatives.189 Because excessive amounts of NbCl5 were found to be required for the reaction to proceed in previous work,185 it was hypothesized that the addition of a Lewis acid would boost the reaction. After a series of explorations, FeCl3 was found to be a good choice, which could be combined with pyrimidines to cause the release of NbCl5 (Scheme 25). Tan and Xiao et al. reported selective synthesis of mesitylene from acetone over a tantalum phosphate catalyst.190 In addition to alkylation, Hara et al. used niobic acid in allylation as a heterogeneous Lewis acid catalyst. This catalyst was useful for the allylation of benzaldehyde with tetraallyl tin; moreover, the conversion of glucose into HMF was realized in water.191

2.4.2. Polymerization

Polyolefinic materials have many marked properties, which make them practical in our daily life. Due to the importance of polyolefin materials, a great deal of research has been done to develop high-performance olefin polymerization catalysts. A large number of new high-activity catalysts based on various transition metals have been discovered.192 In recent years, some chemists have tried to design new catalysts using group VB elements for catalytic polymerization.

Ishii et al. synthesized group VB metal complexes with an [OSSO]-type bis(phenolate) as ligand. The tantalum(V) complex 45 (Figure 4) worked as the first group VB metal catalyst for α-olefin polymerization. Isospecific polymers were obtained with narrow molecular weight and polydispersity using catalyst 45 (Figure 4).193

Figure 4.

Figure 4

Open in a new tab

Catalysts for polymerization

Long and Li et al. synthesized a series of novel vanadium(III) complexes 46 (Figure 4) with bidentate phenoxy-phosphine oxide as ligand.194 These catalysts displayed high thermal stability and high catalytic activities for ethylene polymerization. The most significant advantage of the catalyst is producing polymers with unimodal molecular weight distributions in a high weight range. The copolymerization between ethylene and 1-hexene was also studied.

Wu and Zhang et al. introduced various vanadium complexes 47 (Figure 4) with N-heterocyclic carbene scaffold for ethylene/propylene copolymerization.195 Białek and Bisz synthesized vanadium complexes,196 which was demonstrated to be active for ethylene and 1-octene isospecific polymerization (Mw∼ 1 × 106 g/mol, Mw/Mn = 1.4–2.0).

Nomura’s group found that (arylimido)vanadium(V)–alkylidene complexes 48 and 49(197,198) showed significant catalytic activities for ring-opening metathesis polymerization (ROMP) of various cyclic olefins in 2016 (Scheme 26). The catalytic system had good tolerance to many substrates, and its activity was improved at high temperature. The obtained polymer has a high molecular weight with uniform distribution (Mn = 10 500–39 500, Mw/Mn = 1.34–1.84).

Scheme 26. ROMP Catalyzed by Vanadium Catalysts.

Scheme 26

Open in a new tab

Taniguchi, Asakawa, Maeda, and co-workers systematically investigated the polymerization of diphenylacetylenes with low-valent Ta species (Scheme 27), which were formed in situ after reduction of TaCl5.199 The mechanism of TaCl5–Ph4Sn system is an insertion ring expansion. The polymeric degree produced by this system was much higher than that with the WCl6–Ph4Sn system, and the best result was Mn = 22.0 × 104, Mw/Mn = 2.31.

Scheme 27. Polymerization of Diphenylacetylenes.

Scheme 27

Open in a new tab

2.4.3. Protein Synthesis

Amides are the most important functional groups in many fields. Owing to their importance, the development of efficient amidation processes is an urgent subject.200 Under the circumstances, catalytic synthesis of amides has attracted considerable attention, and a number of catalytic methods (including metal catalysis) have been designed.201−206

Yamamoto et al. have developed several synthetic strategies based on a substrate orientation approach to address the racemization in reactions and reduce contamination due to byproduct generation. First, they attempted using a tantalum alkoxide as Lewis acid catalyst and a hydroxyl group as the guiding group to form amides (Scheme 28a).207 This method can provide dipeptide with up to 97% yield and effectively avoid the racemic problem. But one problem is the narrow range of suitable substrates (only Ser, Thr, and their derivatives). Subsequently, they extended the hydroxyl orientation strategy to solventless amidation catalyzed by a niobium complex (Scheme 28b).208 The products obtained by this method can be converted into dipeptide or tripeptide by simple hydrogenation. Soon after, a Lewis acid catalyzed amide bond synthesis method was proposed, which has strong functional group tolerance (Scheme 28c).209 This tantalum-catalyzed method also can be exploited in the synthesis of tri- and tetrapeptides. However, this method was not suitable for β-homoamino acid methyl esters. Because of the unique properties of β-amino acids and β-peptides, another Lewis acid catalysis approach was proposed for the preparation of peptides suitable for a wide range of substrates (Scheme 28d).210 These methods provide novel and convenient methods for the synthesis of peptide compounds.

Scheme 28. Amidation Reactions Catalyzed by Nb, Ta Catalysts.

Scheme 28

Open in a new tab

3. Inorganic Synthesis

3.1. Water Splitting

Solar water splitting has attracted lots of attention because it can convert solar energy into chemical energy compared to traditional power generation.211 Water splitting using a photocatalyst is an attractive solution for the supply of clean and recyclable hydrogen energy. Tantalum-based semiconductors211 and transition-metal oxynitrides212 are common photocatalysts. Some successful results have been reported for the generation of hydrogen and oxygen from water catalyzed by TaON with high photocatalytic activity.212

With the same structral characters as Nb2O5, Ta2O5 and some tantalates such as NaTaO3 can work as highly active photocatalysts after proper modification.

Domen et al. found tantalum oxynitride, TaON was an efficient photocatalyst driven by visible light. In particular, TaON is very effective for photooxidation of water into O2 while showing low activity for H2 evolution.213 Before long, Nakato et al. also used TaON as active photocatalysts in water photooxidation.214 It was demonstrated that the photocatalytic O2 evolution occurred from a suspension of Ta-complex in the presence of Fe3+. In their report, Fe3+ worked as electron acceptor instead of Ag+ in the previous work. They also utilized in situ photoinduced MIR-IR to explore the mechanism of gas evolution, probing HOOH was vital intermediate.

Tantalum nitride, Ta3N5, is a novel photocatalyst which can be applied under visible light. Domen et al. reported Ta3N5 as a photocatalyst to decompose water under visible light.215 The photocatalytic activity of Ta3N5 for O2 evolution from AgNO3 solution was higher than that for evolution of H2 from AgNO3 solution. The presence of Ag+ as a sacrificial electron acceptor promotes the reaction.

It was also investigated a two-step photocatalytic water splitting system consisting of a modified ZrO2/TaON species, acting as a H2 evolution, an O2 evolution photocatalyst, and a reversible donor/acceptor pair.216,217 This system realized stoichiometric water splitting into H2 and O2 under visible light and an apparent quantum yield of 6.3% under optimal conditions. It was the highest reported value to date for a nonsacrificial visible-light-driven water splitting system. In 2007, Maeda, Domen, and co-worker successfully achieved visible light driven water decomposition by using nonoxide species with d0 electron configuration.218

4. Conclusion

The recent applications of group VB metal elements in organic and inorganic synthesis have been summarized, and it is glaringly obvious that a great variety of reactions can work smoothly in the presence of group VB metals. In most reactions, the mechanism was well studied, while the character of the metal or its complex was fully illustrated. It provides researchers valuable information to develop more potential applications. As we all know, organometallic catalysis is developing rapidly because of its unique advantages in chemical bond cleavage and formation. However, compared to other transition metals, the fifth group of metal elements has not received so much attention. Throughout this Review, the fifth group metals are ideal objects as industrial catalysts. They have the advantages of low price, safety, and diversity. Further development of group VB metals is worth expecting.

Acknowledgments

We gratefully acknowledge the platform support from Zhejiang International Scientific & Technological Cooperation Base of Development and Utilization of Nature Products.

Data Availability Statement

The data underlying this study are available in the published article.

Author Contributions

The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. CRediT: Xinru Xu writing-original draft (lead).

This research was funded by NSFC (22101255), Key Research and Development Program of Zhejiang (2021C03084), High-Level Talent Special Support Plan of Zhejiang Province (2019R52009), and Zhejiang University of Technology (2020414801729).

The authors declare no competing financial interest.

References

  1. Zhang X.; Ma W.; Zhang J.; Tang W.; Xue D.; Xiao J.; Sun H.; Wang C. Asymmetric Ruthenium-Catalyzed Hydroalkylation of Racemic Allylic Alcohols for the Synthesis of Chiral Amino Acid Derivatives. Angew. Chem., Int. Ed. 2022, 61, e202203244. 10.1002/anie.202203244. [DOI] [PubMed] [Google Scholar]
  2. Korvorapun K.; Moselage M.; Struwe J.; Rogge T.; Messinis A. M.; Ackermann L. Regiodivergent C-H and Decarboxylative C-C Alkylation by Ruthenium Catalysis: Ortho Versus Meta Position-Selectivity. Angew. Chem., Int. Ed. 2020, 59, 18795–18803. 10.1002/anie.202007144. [DOI] [PMC free article] [PubMed] [Google Scholar]
  3. Jiang Z. T.; Huang J.; Zeng Y.; Hu F.; Xia Y. Rhodium Catalyzed Regioselective C-H Allylation of Simple Arenes via C-C Bond Activation of Gem-difluorinated Cyclopropanes. Angew. Chem., Int. Ed. 2021, 60, 10626–10631. 10.1002/anie.202016258. [DOI] [PubMed] [Google Scholar]
  4. Li X.; Qi X.; Hou C.; Chen P.; Liu G. Palladium(II)-Catalyzed Enantioselective Azidation of Unactivated Alkenes. Angew. Chem., Int. Ed. 2020, 59, 17239–17244. 10.1002/anie.202006757. [DOI] [PubMed] [Google Scholar]
  5. Liu X. T.; Han X. Y.; Wu Y.; Sun Y. Y.; Gao L.; Huang Z.; Zhang Q. W. Ni-Catalyzed Asymmetric Hydrophosphination of Unactivated Alkynes. J. Am. Chem. Soc. 2021, 143, 11309–11316. 10.1021/jacs.1c05649. [DOI] [PubMed] [Google Scholar]
  6. Zhu Z.; Xiao J.; Li M.; Shi Z. Nickel-Catalyzed Intermolecular Asymmetric Addition of Aryl Iodides across Aldehydes. Angew. Chem., Int. Ed. 2022, 61, e202201370. 10.1002/anie.202201370. [DOI] [PubMed] [Google Scholar]
  7. Wang C.; Huang K.; Ye J.; Duan W. L. Asymmetric Synthesis of P-Stereogenic Secondary Phosphine-Boranes by an Unsymmetric Bisphosphine Pincer-Nickel Complex. J. Am. Chem. Soc. 2021, 143, 5685–5690. 10.1021/jacs.1c02772. [DOI] [PubMed] [Google Scholar]
  8. Li Y. B.; Tian H.; Yin L. Copper(I)-Catalyzed Asymmetric 1,4-Conjugate Hydrophosphination of α,β-Unsaturated Amides. J. Am. Chem. Soc. 2020, 142, 20098–20106. 10.1021/jacs.0c09654. [DOI] [PubMed] [Google Scholar]
  9. Zhang Y. F.; Dong X. Y.; Cheng J. T.; Yang N. Y.; Wang L. L.; Wang F. L.; Luan C.; Liu J.; Li Z. L.; Gu Q. S.; Liu X. Y. Enantioconvergent Cu-Catalyzed Radical C-N Coupling of Racemic Secondary Alkyl Halides to Access α-Chiral Primary Amines. J. Am. Chem. Soc. 2021, 143, 15413–15419. 10.1021/jacs.1c07726. [DOI] [PubMed] [Google Scholar]
  10. Lv D.; Sun Q.; Zhou H.; Ge L.; Qu Y.; Li T.; Ma X.; Li Y.; Bao H. Iron-Catalyzed Radical Asymmetric Aminoazidation and Diazidation of Styrenes. Angew. Chem., Int. Ed. 2021, 60, 12455–12460. 10.1002/anie.202017175. [DOI] [PubMed] [Google Scholar]
  11. Braconi E.; Cramer N. Crossed Regio- and Enantioselective Iron-Catalyzed [4 + 2]-Cycloadditions of Unactivated Dienes. Angew. Chem., Int. Ed. 2022, 61, e202112148. 10.1002/anie.202112148. [DOI] [PMC free article] [PubMed] [Google Scholar]
  12. Herraiz A. G.; Cramer N. Cobalt(III)-Catalyzed Diastereo- and Enantioselective Three-Component C-H Functionalization. ACS Catal. 2021, 11, 11938–11944. 10.1021/acscatal.1c03153. [DOI] [Google Scholar]
  13. Chen C.; Wang H.; Li T.; Lu D.; Li J.; Zhang X.; Hong X.; Lu Z. Cobalt-Catalyzed Asymmetric Sequential Hydroboration/Isomerization/Hydroboration of 2-Aryl Vinylcyclopropanes. Angew. Chem., Int. Ed. 2022, 61, e202205619. 10.1002/anie.202205619. [DOI] [PubMed] [Google Scholar]
  14. Sakunthala A.; Reddy M. V.; Selvasekarapandian S.; Chowdari B. V. R.; Selvin P. C. Energy Storage Studies of Bare and Doped Vanadium Pentoxide, (V1.95M0.05)O5, M = Nb, Ta, for Lithium Ion Batteries. Energy Environ. Sci. 2011, 4, 1712–1725. 10.1039/c0ee00513d. [DOI] [Google Scholar]
  15. Chia X.; Ambrosi A.; Lazar P.; Sofer Z.; Pumera M. Electrocatalysis of Layered Group 5 Metallic Transition Metal Dichalcogenides (MX2, M = V, Nb, And Ta; X = S, Se, And Te). J. Mater. Chem. A 2016, 4, 14241–14253. 10.1039/C6TA05110C. [DOI] [Google Scholar]
  16. Wan B.; Xiao F.; Zhang Y.; Zhao Y.; Wu L.; Zhang J.; Gou H. Theoretical Study of Structural Characteristics, Mechanical Properties and Electronic Structure of Metal (TM = V, Nb And Ta) Silicides. J. Alloys Compd. 2016, 681, 412–420. 10.1016/j.jallcom.2016.04.253. [DOI] [Google Scholar]
  17. Wei Z.; Junge K.; Beller M.; Jiao H. Exploring the Activities of Vanadium, Niobium, and Tantalum PNP Pincer Complexes in The Hydrogenation of Phenyl-Substituted C≡N, C=N, C≡C, C=C, and C=O Functional Groups. C. R. Chimie 2018, 21, 303–309. 10.1016/j.crci.2017.09.001. [DOI] [Google Scholar]
  18. Galloni P.; Conte V.; Floris B. A Journey into The Electrochemistry of Vanadium Compounds. Coordin. Chem. Rev. 2015, 301, 240–299. 10.1016/j.ccr.2015.02.022. [DOI] [Google Scholar]
  19. Makinen M. W.; Salehitazangi M. The Structural Basis of Action of Vanadyl (VO2) Chelates in Cells. Coordin. Chem. Rev. 2014, 279, 1–22. 10.1016/j.ccr.2014.07.003. [DOI] [PMC free article] [PubMed] [Google Scholar]
  20. Leblanc C.; Vilter H.; Fournier J. B.; Delage L.; Potin P.; Rebuffet E.; Michel G.; Solari P. L.; Feiters M. C.; Czjzek M. Vanadium Haloperoxidases: from The Discovery 30 Years Ago to X-Ray Crystallographic and V K-Edge Absorption Spectroscopic Studies. Coordin. Chem. Rev. 2015, 301, 134–146. 10.1016/j.ccr.2015.02.013. [DOI] [Google Scholar]
  21. Costa Pessoa J.; Garribba E.; Santos M. F.A.; Santos-Silva T. Vanadium and Proteins: Uptake, Transport, Structure, Activity and Function. Coordin. Chem. Rev. 2015, 301, 49–86. 10.1016/j.ccr.2015.03.016. [DOI] [Google Scholar]
  22. McLauchlan C. C.; Peters B. J.; Willsky G. R.; Crans D. C. Vanadium-Phosphatase Complexes: Phosphatase Inhibitors Favor The Trigonal Bipyramidal Transition State Geometries. Coordin. Chem. Rev. 2015, 301, 163–199. 10.1016/j.ccr.2014.12.012. [DOI] [Google Scholar]
  23. Wever R.; van der Horst M. A. The Role of Vanadium Haloperoxidases in The Formation of Volatile Brominated Compounds and Their Impact on The Environment. Dalton Trans. 2013, 42, 11778–11786. 10.1039/c3dt50525a. [DOI] [PubMed] [Google Scholar]
  24. Kioseoglou E.; Petanidis S.; Gabriel C.; Salifoglou A. The Chemistry and Biology of Vanadium Compounds in Cancer Therapeutics. Coordin. Chem. Rev. 2015, 301, 87–105. 10.1016/j.ccr.2015.03.010. [DOI] [Google Scholar]
  25. Pessoa J. C.; Etcheverry S.; Gambino D. Vanadium Compounds in Medicine. Coordin. Chem. Rev. 2015, 301, 24–48. 10.1016/j.ccr.2014.12.002. [DOI] [PMC free article] [PubMed] [Google Scholar]
  26. Costa Pessoa J.; Maurya M. R. Vanadium Complexes Supported on Organic Polymers as Sustainable Systems for Catalytic Oxidations. Inorg. Chim. Acta 2017, 455, 415–428. 10.1016/j.ica.2016.04.012. [DOI] [Google Scholar]
  27. Chieregato A.; Nieto J. M. L.; Cavani F. Mixed-Oxide Catalysts with Vanadium as The Key Element for Gas-Phase Reactions. Coordin. Chem. Rev. 2015, 301, 3–23. 10.1016/j.ccr.2014.12.003. [DOI] [Google Scholar]
  28. Artiglia L.; Agnoli S.; Granozzi G. Vanadium Oxide Nanostructures on Another Oxide: The Viewpoint from Model Catalysts Studies. Coordin. Chem. Rev. 2015, 301, 106–122. 10.1016/j.ccr.2014.12.015. [DOI] [Google Scholar]
  29. Amadio E.; Di Lorenzo R.; Zonta C.; Licini G. Vanadium Catalyzed Aerobic Carbon-Carbon Cleavage. Coordin. Chem. Rev. 2015, 301, 147–162. 10.1016/j.ccr.2015.06.004. [DOI] [Google Scholar]
  30. Sutradhar M.; Martins L. M. D. R. S.; da Silva M. F. C. G.; Pombeiro A. J. L. Vanadium Complexes: Recent Progress In Oxidation Catalysis. Coordin. Chem. Rev. 2015, 301, 200–239. 10.1016/j.ccr.2015.01.020. [DOI] [Google Scholar]
  31. Parker K. D. J.; Fryzuk M. D. Synthesis, Structure, and Reactivity of Niobium and Tantalum Alkyne Complexes. Organometallics 2015, 34, 2037–2047. 10.1021/om5010385. [DOI] [Google Scholar]
  32. Gomez M.; Hernandez-Prieto C.; Martin A.; Mena M.; Santamaria C. An Effective Route to Dinuclear Niobium and Tantalum Imido Complexes. Inorg. Chem. 2017, 56, 11681–11687. 10.1021/acs.inorgchem.7b01652. [DOI] [PubMed] [Google Scholar]
  33. Kawakita K.; Kakiuchi Y.; Beaumier E. P.; Tonks I. A.; Tsurugi H.; Mashima K. Synthesis of Pyridylimido Complexes of Tantalum and Niobium by Reductive Cleavage of the N = N Bond of 2,2′-Azopyridine: Precursors for Early-Late Heterobimetallic Complexes. Inorg. Chem. 2019, 58, 15155–15165. 10.1021/acs.inorgchem.9b02043. [DOI] [PMC free article] [PubMed] [Google Scholar]
  34. Liu D.; Zhang A.; Jia J.; Meng J.; Su B. Phase Evolution and Properties of (VNbTaMoW)C High Entropy Carbide Prepared by Reaction Synthesis. J. Eur. Ceram. Soc. 2020, 40, 2746–2751. 10.1016/j.jeurceramsoc.2020.03.020. [DOI] [Google Scholar]
  35. Unkrig W.; Schmitt M.; Kratzert D.; Himmel D.; Krossing I. Synthesis and Characterization of Crystalline Niobium and Tantalum Carbonyl Complexes at Room Temperature. Nat. Chem. 2020, 12, 647–653. 10.1038/s41557-020-0487-3. [DOI] [PubMed] [Google Scholar]
  36. Wei R.; Hu J.; Chen X.; Gong Y. Vanadium, Niobium and Tantalum Complexes with Terminal Sulfur Radical Ligands. Dalton Trans. 2021, 50, 11300–11306. 10.1039/D1DT01956B. [DOI] [PubMed] [Google Scholar]
  37. Ziolek M.; Sobczak I. The Role of Niobium Component in Heterogeneous Catalysts. Catal. Today 2017, 285, 211–225. 10.1016/j.cattod.2016.12.013. [DOI] [Google Scholar]
  38. Silva T. C.; Pires M. D.; de Castro A. A.; Lacerda L. C. T.; Rocha M. V. J.; Ramalho T. C. Structure and Bonding in NbX5 X = (F, Cl, Br And I) Complexes: A Molecular Orbital Perspective in The C-H Bond Activation. Theor. Chem. Acc. 2018, 137, 146. 10.1007/s00214-018-2348-3. [DOI] [Google Scholar]
  39. Petit J.; Magna L.; Mézailles N. Alkene Oligomerization via Metallacycles: Recent Advances and Mechanistic Insights. Coordin. Chem. Rev. 2022, 450, 214227. 10.1016/j.ccr.2021.214227. [DOI] [Google Scholar]
  40. Fulton J. R. Vanadium, Niobium and Tantalum. Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem. 2013, 109, 108–118. 10.1039/c3ic90021e. [DOI] [Google Scholar]
  41. Rej S.; Tsurugi H.; Mashima K. Multiply-Bonded Dinuclear Complexes of Early-Transition Metals as Minimum Entities of Metal Cluster Catalysts. Coordin. Chem. Rev. 2018, 355, 223–239. 10.1016/j.ccr.2017.08.016. [DOI] [Google Scholar]
  42. Dawood K. M.; Nomura K. Recent Developments in Z-Selective Olefin Metathesis Reactions by Molybdenum, Tungsten, Ruthenium, and Vanadium Catalysts. Adv. Synth. Catal. 2021, 363, 1970–1997. 10.1002/adsc.202001117. [DOI] [Google Scholar]
  43. Guerrero-Pérez M. O. The Fascinating Effect of Niobium as Catalytic Promoting Agent. Catal. Today 2020, 354, 19–25. 10.1016/j.cattod.2019.04.008. [DOI] [Google Scholar]
  44. Fulton J. R. Vanadium, Niobium and Tantalum. Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem. 2009, 105, 188–200. 10.1039/b818156j. [DOI] [Google Scholar]
  45. Langeslay R. R.; Kaphan D. M.; Marshall C. L.; Stair P. C.; Sattelberger A. P.; Delferro M. Catalytic Applications of Vanadium: A Mechanistic Perspective. Chem. Rev. 2019, 119, 2128–2191. 10.1021/acs.chemrev.8b00245. [DOI] [PubMed] [Google Scholar]
  46. Sokolov M. N.; Fedin V. P. Chalcogenide Clusters of Vanadium, Niobium and Tantalum. Coordin. Chem. Rev. 2004, 248, 925–944. 10.1016/j.ccr.2004.03.021. [DOI] [Google Scholar]
  47. Ghosh S.; Roy D. K. Group 5 Metal-Metal Bonds. Molecular Metal-Metal Bonds 2015, 91–137. 10.1002/9783527673353.ch5. [DOI] [Google Scholar]
  48. Grice K. A. Carbon Dioxide Reduction with Homogenous Early Transition Metal Complexes: Opportunities and Challenges for Developing CO2 Catalysis. Coordin. Chem. Rev. 2017, 336, 78–95. 10.1016/j.ccr.2017.01.007. [DOI] [Google Scholar]
  49. Bayot D.; Devillers M. Peroxo Complexes of Niobium(V) and Tantalum(V). Coordin. Chem. Rev. 2006, 250, 2610–2626. 10.1016/j.ccr.2006.04.011. [DOI] [Google Scholar]
  50. Dichmann K.; Hamer G.; Nyburg S. C.; Reynolds W. F. The 2:1 Vanadyl Acetylacetonate: 1,4-Dioxan Complex. A Nuclear Magnetic Resonance and X-Ray Crystal Structure Study. J. Chem. Soc. D 1970, 1295–1296. 10.1039/c29700001295. [DOI] [Google Scholar]
  51. Michaelson R. C.; Palermo R. E.; Sharpless K. B. Chiral Hydroxamic Acids as Ligands in The Vanadium Catalyzed Asymmetric Epoxidation of Allylic Alcohols by Tert-Butyl Hydroperoxide. J. Am. Chem. Soc. 1977, 99, 1990–1992. 10.1021/ja00448a059. [DOI] [Google Scholar]
  52. Sharpless K. B.; Michaelson R. C. High Stereo- and Regioselectivities in The Transition Metal Catalyzed Epoxidations of Olefinic Alcohols by Tert-Butyl Hydroperoxide. J. Am. Chem. Soc. 1973, 95, 6136–6137. 10.1021/ja00799a061. [DOI] [Google Scholar]
  53. Tanaka S.; Yamamoto H.; Nozaki H.; Sharpless K. B.; Michaelson R. C.; Cutting J. D. Stereoselective Epoxidations of Acyclic Allylic Alcohols by Transition Metal-Hydroperoxide Reagents. Synthesis of Dl-C18 Cecropia Juvenile Hormone from Farnesol. J. Am. Chem. Soc. 1974, 96, 5254–5255. 10.1021/ja00823a042. [DOI] [PubMed] [Google Scholar]
  54. Rossiter B. E.; Verhoeven T. R.; Sharpless K. B. Stereoselective Epoxidation of Acyclic Allylic Alcohols. A Correction of Our Previous Work. Tetrahedron Lett. 1979, 20, 4733–4736. 10.1016/S0040-4039(01)86696-X. [DOI] [Google Scholar]
  55. Murase N.; Hoshino Y.; Oishi M.; Yamamoto H. Chiral Vanadium-Based Catalysts for Asymmetric Epoxidation of Allylic Alcohols. J. Org. Chem. 1999, 64, 338–339. 10.1021/jo9821933. [DOI] [Google Scholar]
  56. Hoshino Y.; Murase N.; Oishi M.; Yamamoto H. Design of Optically Active Hydroxamic Acids as Ligands in Vanadium-Catalyzed Asymmetric Epoxidation. Bull. Chem. Soc. Jpn. 2000, 73, 1653–1658. 10.1246/bcsj.73.1653. [DOI] [Google Scholar]
  57. Hoshino Y.; Yamamoto H. Novel α-Amino Acid-Based Hydroxamic Acid Ligands for Vanadium-Catalyzed Asymmetric Epoxidation of Allylic Alcohols. J. Am. Chem. Soc. 2000, 122, 10452–10453. 10.1021/ja002602o. [DOI] [Google Scholar]
  58. Makita N.; Hoshino Y.; Yamamoto H. Asymmetric Epoxidation of Homoallylic Alcohols and Application in A Concise Total Synthesis of (−)-α-Bisabolol and (−)-8-Epi-α-Bisabolol. Angew. Chem., Int. Ed. 2003, 42, 941–943. 10.1002/anie.200390250. [DOI] [PubMed] [Google Scholar]
  59. Zhang W.; Basak A.; Kosugi Y.; Hoshino Y.; Yamamoto H. Enantioselective Epoxidation of Allylic Alcohols by A Chiral Complex of Vanadium: An Effective Controller System and A Rational Mechanistic Model. Angew. Chem., Int. Ed. 2005, 44, 4389–4391. 10.1002/anie.200500938. [DOI] [PubMed] [Google Scholar]
  60. Zhang W.; Yamamoto H. Vanadium-Catalyzed Asymmetric Epoxidation of Homoallylic Alcohols. J. Am. Chem. Soc. 2007, 129, 286–287. 10.1021/ja067495y. [DOI] [PMC free article] [PubMed] [Google Scholar]
  61. Li Z.; Zhang W.; Yamamoto H. Vanadium-Catalyzed Enantioselective Desymmetrization of Meso Secondary Allylic Alcohols and Homoallylic Alcohols. Angew. Chem., Int. Ed. 2008, 47, 7520–7522. 10.1002/anie.200802523. [DOI] [PMC free article] [PubMed] [Google Scholar]
  62. Li F.; Wang Z. H.; Zhao L.; Xiong F. J.; He Q. Q.; Chen F. E. An Efficient Enantioselective Synthesis of Florfenicol via A Vanadium-Catalyzed Asymmetric Epoxidation. Tetrahedron Asymmetry 2011, 22, 1337–1341. 10.1016/j.tetasy.2011.07.011. [DOI] [Google Scholar]
  63. Malkov A. V.; Czemerys L.; Malyshev D. A. Vanadium-Catalyzed Asymmetric Epoxidation of Allylic Alcohols in Water. J. Org. Chem. 2009, 74, 3350–3355. 10.1021/jo900294h. [DOI] [PubMed] [Google Scholar]
  64. Yoon T. P.; Jacobsen E. N. Privileged Chiral Catalysts. Science 2003, 299, 1691–1693. 10.1126/science.1083622. [DOI] [PubMed] [Google Scholar]
  65. Teichert J. F.; Feringa B. L. Phosphoramidites: Privileged Ligands in Asymmetric Catalysis. Angew. Chem., Int. Ed. 2010, 49, 2486–2528. 10.1002/anie.200904948. [DOI] [PubMed] [Google Scholar]
  66. Noji M.; Kobayashi T.; Uechi Y.; Kikuchi A.; Kondo H.; Sugiyama S.; Ishii K. Asymmetric Epoxidation of Allylic Alcohols Catalyzed by Vanadium-Binaphthylbishydroxamic Acid Complex. J. Org. Chem. 2015, 80, 3203–3210. 10.1021/acs.joc.5b00185. [DOI] [PubMed] [Google Scholar]
  67. Egami H.; Oguma T.; Katsuki T. Oxidation Catalysis of Nb(Salan) Complexes: Asymmetric Epoxidation of Allylic Alcohols Using Aqueous Hydrogen Peroxide as An Oxidant. J. Am. Chem. Soc. 2010, 132, 5886–5895. 10.1021/ja100795k. [DOI] [PubMed] [Google Scholar]
  68. Matsumoto K.; Sawada Y.; Katsuki T. Asymmetric Epoxidation of Olefins Catalyzed by Ti(Salan) Complexes Using Aqueous Hydrogen Peroxide as The Oxidant. Pure Appl. Chem. 2008, 80, 1071–1077. 10.1351/pac200880051071. [DOI] [Google Scholar]
  69. Sako M.; Takeuchi Y.; Tsujihara T.; Kodera J.; Kawano T.; Takizawa S.; Sasai H. Efficient Enantioselective Synthesis of Oxahelicenes Using Redox/Acid Cooperative Catalysts. J. Am. Chem. Soc. 2016, 138, 11481–11484. 10.1021/jacs.6b07424. [DOI] [PubMed] [Google Scholar]
  70. Carreno M. C. Applications of Sulfoxides to Asymmetric-Synthesis of Biologically-Active Compounds. Chem. Rev. 1995, 95, 1717–1760. 10.1021/cr00038a002. [DOI] [Google Scholar]
  71. Bolm C.; Simic O. Highly Enantioselective Hetero-Diels-Alder Reactions Catalyzed by A C2-Symmetric Bis(Sulfoximine) Copper(II) Complex. J. Am. Chem. Soc. 2001, 123, 3830–3831. 10.1021/ja004261k. [DOI] [PubMed] [Google Scholar]
  72. Bizet V.; Kowalczyk R.; Bolm C. Fluorinated Sulfoximines: Syntheses, Properties and Applications. Chem. Soc. Rev. 2014, 43, 2426–2438. 10.1039/c3cs60427f. [DOI] [PubMed] [Google Scholar]
  73. Cheng H. G.; Feng B.; Chen L. Y.; Guo W.; Yu X. Y.; Lu L. Q.; Chen J. R.; Xiao W. J. Rational Design of Sulfoxide-Phosphine Ligands for Pd-Catalyzed Enantioselective Allylic Alkylation Reactions. Chem. Commun. 2014, 50, 2873–2875. 10.1039/C3CC49488H. [DOI] [PubMed] [Google Scholar]
  74. Trost B. M.; Rao M. Development of Chiral Sulfoxide Ligands for Asymmetric Catalysis. Angew. Chem., Int. Ed. 2015, 54, 5026–5043. 10.1002/anie.201411073. [DOI] [PubMed] [Google Scholar]
  75. Jia T.; Wang M.; Liao J. Chiral Sulfoxide Ligands in Asymmetric Catalysis. Top. Curr. Chem. 2019, 377, 8. 10.1007/s41061-019-0232-9. [DOI] [PubMed] [Google Scholar]
  76. Butler A.; Clague M. J.; Meister G. E. Vanadium Peroxide Complexes. Chem. Rev. 1994, 94, 625–638. 10.1021/cr00027a004. [DOI] [Google Scholar]
  77. Bolm C. Vanadium-Catalyzed Asymmetric Oxidations. Coordin. Chem. Rev. 2003, 237, 245–256. 10.1016/S0010-8545(02)00249-7. [DOI] [Google Scholar]
  78. Conte V.; Coletti A.; Floris B.; Licini G.; Zonta C. Mechanistic Aspects of Vanadium Catalysed Oxidations with Peroxides. Coordin. Chem. Rev. 2011, 255, 2165–2177. 10.1016/j.ccr.2011.03.006. [DOI] [Google Scholar]
  79. Nakajima K.; Kojima M.; Fujita J. Asymmetric Oxidation of Sulfides to Sulfoxides by Organic Hydroperoxides with Optically Active Schiff Base-Oxovanadium(IV) Catalysts. Chem. Lett. 1986, 15, 1483–1486. 10.1246/cl.1986.1483. [DOI] [Google Scholar]
  80. Nakajima K.; Kojima K.; Kojima M.; Fujita J. Preparation and Characterization of Optically Active Schiff Base-Oxovanadium(IV) and -Oxovanadium(V) Complexes and Catalytic Properties of These Complexes on Asymmetric Oxidation of Sulfides into Sulfoxides with Organic Hydroperoxides. Bull. Chem. Soc. Jpn. 1990, 63, 2620–2630. 10.1246/bcsj.63.2620. [DOI] [Google Scholar]
  81. Nakajima K.; Kojima M.; Toriumi K.; Saito K.; Fujita J. Crystal Structures of [VO(sal-L-ala)(OCH3)(CH3OH)] (sal-L-ala = N-salicylidene-L-alaninate) and {[VO(sal-L-ala)]2O}2·2CH2Cl2, and the Catalytic Activity of These and Related Complexes on Asymmetric Oxidation of Methyl Phenyl Sulfide witht-Butyl Hydroperoxide. Bull. Chem. Soc. Jpn. 1989, 62, 760–767. 10.1246/bcsj.62.760. [DOI] [Google Scholar]
  82. Bolm C.; Bienewald F. Asymmetrische Sulfid-Oxidation mit Vanadium-Katalysatoren und H2O2. Angew. Chem. 1995, 107, 2883–2885. 10.1002/ange.19951072317. [DOI] [Google Scholar]
  83. Boln C.; Luong T. K. K.; Harms K. Bis[2-(oxazolinyl)phenolato]oxovanadium(IV) Complexes: Syntheses, Crystal Structures and Catalyses. Chem. Ber. 1997, 130, 887–890. 10.1002/cber.19971300712. [DOI] [Google Scholar]
  84. Wang Y.; Wang M.; Wang Y.; Wang X.; Wang L.; Sun L. Highly Enantioselective Sulfoxidation with Vanadium Catalysts of Schiff Bases Derived from Bromo- and Iodo-Functionalized Hydroxynaphthaldehydes. J. Catal. 2010, 273, 177–181. 10.1016/j.jcat.2010.05.013. [DOI] [Google Scholar]
  85. Stingl K. A.; Weiß K. M.; Tsogoeva S. B. Asymmetric Vanadium- and Iron-Catalyzed Oxidations: New Mild (R)-Modafinil Synthesis and Formation of Epoxides Using Aqueous H2O2 as A Terminal Oxidant. Tetrahedron 2012, 68, 8493–8501. 10.1016/j.tet.2012.07.052. [DOI] [Google Scholar]
  86. Lazar A.; Sharma P.; Singh A. P. Chiral VIVO-Sal-Indanol Complex over Modified SBA-15: An Efficient, Reusable Enantioselective Catalyst for Asymmetric Sulfoxidation. Microporous Mesoporous Mater. 2013, 170, 331–339. 10.1016/j.micromeso.2012.12.014. [DOI] [Google Scholar]
  87. Rostami A.; Atashkar B. Chiral Oxo-Vanadium (+)-Pseudoephedrine Complex Immobilized on Magnetic Nanoparticles: A Highly Efficient and Recyclable Novel Nanocatalyst for The Chemoselective Oxidation of Sulfides to Sulfoxides Using H2O2. J. Mol. Catal. A Chem. 2015, 398, 170–176. 10.1016/j.molcata.2014.12.010. [DOI] [Google Scholar]
  88. Pordea A.; Creus M.; Panek J.; Duboc C.; Mathis D.; Novic M.; Ward T. R. Artificial Metalloenzyme for Enantioselective Sulfoxidation Based on Vanadyl-Loaded Streptavidin. J. Am. Chem. Soc. 2008, 130, 8085–8088. 10.1021/ja8017219. [DOI] [PubMed] [Google Scholar]
  89. Zhang D.; Dutasta J.-P.; Dufaud V.; Guy L.; Martinez A. Sulfoxidation inside a C3-Vanadium(V) Bowl-Shaped Catalyst. ACS Catal. 2017, 7, 7340–7345. 10.1021/acscatal.7b01886. [DOI] [Google Scholar]
  90. Shen C.; Qiao J.; Zhao L. W.; Zheng K.; Jin J. Z.; Zhang P. F. An Efficient Silica Supported Chitosan@Vanadium Catalyst for Asymmetric Sulfoxidation and Its Application in The Synthesis of Esomeprazole. Catal. Commun. 2017, 92, 114–118. 10.1016/j.catcom.2017.01.018. [DOI] [Google Scholar]
  91. Ishihara K.; Nakamura H.; Yamamoto H. Chiral SEM Ether-Tin Tetrachloride as an Enantioselective Hydroxymethylating Reagent for Silyl Enol Ethers: γ-Effect of Silicon. J. Am. Chem. Soc. 1999, 121, 7720–7721. 10.1021/ja9916613. [DOI] [Google Scholar]
  92. Held F. E.; Grau D.; Tsogoeva S. B. Enantioselective Cycloaddition Reactions Catalyzed by BINOL-Derived Phosphoric Acids and N-Triflyl Phosphoramides: Recent Advances. Molecules 2015, 20, 16103–16126. 10.3390/molecules200916103. [DOI] [PMC free article] [PubMed] [Google Scholar]
  93. Nguyen T. N.; Chen P. A.; Setthakarn K.; May J. A. Chiral Diol-Based Organocatalysts in Enantioselective Reactions. Molecules 2018, 23, 2317. 10.3390/molecules23092317. [DOI] [PMC free article] [PubMed] [Google Scholar]
  94. Kang H.; Herling M. R.; Niederer K. A.; Lee Y. E.; Vasu Govardhana Reddy P.; Dey S.; Allen S. E.; Sung P.; Hewitt K.; Torruellas C.; Kim G. J.; Kozlowski M. C. Enantioselective Vanadium-Catalyzed Oxidative Coupling: Development and Mechanistic Insights. J. Org. Chem. 2018, 83, 14362–14384. 10.1021/acs.joc.8b02083. [DOI] [PMC free article] [PubMed] [Google Scholar]
  95. Sako M.; Takizawa S.; Sasai H. Chiral Vanadium Complex-Catalyzed Oxidative Coupling of Arenols. Tetrahedron 2020, 76, 131645. 10.1016/j.tet.2020.131645. [DOI] [Google Scholar]
  96. Chu C.-Y.; Hwang D.-R.; Wang S.-K.; Uang B.-J. Chiral Oxovanadium Complex Catalyzed Enantioselective Oxidative Coupling of 2-Naphthols. Chem. Commun. 2001, 2001, 980–981. 10.1039/b101670i. [DOI] [Google Scholar]
  97. Hon S. W.; Li C. H.; Kuo J. H.; Barhate N. B.; Liu Y. H.; Wang Y.; Chen C. T. Catalytic Asymmetric Coupling of 2-Naphthols by Chiral Tridentate Oxovanadium(IV) Complexes. Org. Lett. 2001, 3, 869–872. 10.1021/ol015505o. [DOI] [PubMed] [Google Scholar]
  98. Barhate N. B.; Chen C. T. Catalytic Asymmetric Oxidative Couplings of 2-Naphthols by Tridentate N-Ketopinidene-Based Vanadyl Dicarboxylates. Org. Lett. 2002, 4, 2529–2532. 10.1021/ol026156g. [DOI] [PubMed] [Google Scholar]
  99. Luo Z.; Liu Q.; Gong L.; Cui X.; Mi A.; Jiang Y. The Rational Design of Novel Chiral Oxovanadium(IV) Complexes for Highly Enantioselective Oxidative Coupling of 2-Naphthols. Chem. Commun. 2002, 2002, 914–915. 10.1039/b201351g. [DOI] [PubMed] [Google Scholar]
  100. Takizawa S.; Katayama T.; Kameyama C.; Onitsuka K.; Suzuki T.; Yanagida T.; Kawai T.; Sasai H. Chiral Dinuclear Vanadium(V) Catalysts for Oxidative Coupling of 2-Naphthols. Chem. Commun. 2008, 2008, 1810–1812. 10.1039/b717068h. [DOI] [PubMed] [Google Scholar]
  101. Kim H. Y.; Takizawa S.; Sasai H.; Oh K. Reversal of Enantioselectivity Approach to BINOLs via Single and Dual 2-Naphthol Activation Modes. Org. Lett. 2017, 19, 3867–3870. 10.1021/acs.orglett.7b01734. [DOI] [PubMed] [Google Scholar]
  102. Sako M.; Sugizaki A.; Takizawa S. Asymmetric Oxidative Coupling of Hydroxycarbazoles: Facile Synthesis of (+)-Bi-2-Hydroxy-3-Methylcarbazole. Bioorg. Med. Chem. Lett. 2018, 28, 2751–2753. 10.1016/j.bmcl.2018.02.033. [DOI] [PubMed] [Google Scholar]
  103. Sako M.; Aoki T.; Zumbragel N.; Schober L.; Groger H.; Takizawa S.; Sasai H. Chiral Dinuclear Vanadium Complex-Mediated Oxidative Coupling of Resorcinols. J. Org. Chem. 2019, 84, 1580–1587. 10.1021/acs.joc.8b02494. [DOI] [PubMed] [Google Scholar]
  104. Sako M.; Higashida K.; Kamble G. T.; Kaut K.; Kumar A.; Hirose Y.; Zhou D.-Y.; Suzuki T.; Rueping M.; Maegawa T.; Takizawa S.; Sasai H. Chemo- and Enantioselective Hetero-Coupling of Hydroxycarbazoles Catalyzed by A Chiral Vanadium(V) Complex. Org. Chem. Front. 2021, 8, 4878–4885. 10.1039/D1QO00783A. [DOI] [Google Scholar]
  105. Kang H.; Lee Y. E.; Reddy P. V. G.; Dey S.; Allen S. E.; Niederer K. A.; Sung P.; Hewitt K.; Torruellas C.; Herling M. R.; Kozlowski M. C. Asymmetric Oxidative Coupling of Phenols and Hydroxycarbazoles. Org. Lett. 2017, 19, 5505–5508. 10.1021/acs.orglett.7b02552. [DOI] [PMC free article] [PubMed] [Google Scholar]
  106. Ohuchi T.; Miyatake T.; Hitomi Y.; Tanaka T. Liquid Phase Photooxidation of Alcohol over Niobium Oxide without Solvents. Catal. Today 2007, 120, 233–239. 10.1016/j.cattod.2006.07.044. [DOI] [Google Scholar]
  107. Shishido T.; Miyatake T.; Teramura K.; Hitomi Y.; Yamashita H.; Tanaka T. Mechanism of Photooxidation of Alcohol over Nb2O5. J. Phys. Chem. C 2009, 113, 18713–18718. 10.1021/jp901603p. [DOI] [Google Scholar]
  108. Xi G.; Ye J. Synthesis of Bismuth Vanadate Nanoplates with Exposed {001} Facets and Enhanced Visible-Light Photocatalytic Properties. Chem. Commun. 2010, 46, 1893–1895. 10.1039/B923435G. [DOI] [PubMed] [Google Scholar]
  109. Jo W. J.; Jang J. W.; Kong K. J.; Kang H. J.; Kim J. Y.; Jun H.; Parmar K. P.; Lee J. S. Phosphate Doping into Monoclinic Bivo4 for Enhanced Photoelectrochemical Water Oxidation Activity. Angew. Chem., Int. Ed. 2012, 51, 3147–3151. 10.1002/anie.201108276. [DOI] [PubMed] [Google Scholar]
  110. Yuan B.; Chong R.; Zhang B.; Li J.; Liu Y.; Li C. Photocatalytic Aerobic Oxidation of Amines to Imines on BiVO4 under Visible Light Irradiation. Chem. Commun. 2014, 50, 15593–15596. 10.1039/C4CC07097F. [DOI] [PubMed] [Google Scholar]
  111. Furukawa S.; Ohno Y.; Shishido T.; Teramura K.; Tanaka T. Selective Amine Oxidation Using Nb2O5 Photocatalyst and O2. ACS Catal. 2011, 1, 1150–1153. 10.1021/cs200318n. [DOI] [Google Scholar]
  112. Furukawa S.; Ohno Y.; Shishido T.; Teramura K.; Tanaka T. Reaction Mechanism of Selective Photooxidation of Amines over Niobium Oxide: Visible-Light-Induced Electron Transfer between Adsorbed Amine and Nb2O5. J. Phys. Chem. C 2013, 117, 442–450. 10.1021/jp310501h. [DOI] [Google Scholar]
  113. Furukawa S.; Shishido T.; Teramura K.; Tanaka T. Reaction Mechanism of Selective Photooxidation of Hydrocarbons over Nb2O5. J. Phys. Chem. C 2011, 115, 19320–19327. 10.1021/jp207316f. [DOI] [Google Scholar]
  114. Furukawa S.; Shishido T.; Teramura K.; Tanaka T. Photocatalytic Oxidation of Alcohols over TiO2 Covered with Nb2O5. ACS Catal. 2012, 2, 175–179. 10.1021/cs2005554. [DOI] [Google Scholar]
  115. Furukawa S.; Shishido T.; Teramura K.; Tanaka T. Selective Aerobic Oxidation of Primary Alcohols to Aldehydes over Nb2o5 Photocatalyst with Visible Light. ChemPhysChem 2014, 15, 2665–2667. 10.1002/cphc.201402343. [DOI] [PubMed] [Google Scholar]
  116. Tamai K.; Hosokawa S.; Teramura K.; Shishido T.; Tanaka T. Synthesis of Niobium Oxide Nanoparticles with Plate Morphology Utilizing Solvothermal Reaction and Their Performances for Selective Photooxidation. Appl. Catal., B 2016, 182, 469–475. 10.1016/j.apcatb.2015.10.003. [DOI] [Google Scholar]
  117. Tamai K.; Murakami K.; Hosokawa S.; Asakura H.; Teramura K.; Tanaka T. Visible-Light Selective Photooxidation of Aromatic Hydrocarbons via Ligand-to-Metal Charge Transfer Transition on Nb2O5. J. Phys. Chem. C 2017, 121, 22854–22861. 10.1021/acs.jpcc.7b07339. [DOI] [Google Scholar]
  118. De Carvalho G. S. G.; Chagas L. H.; Fonseca C. G.; de Castro P. P.; Sant’Ana A. C.; Leitão A. A.; Amarante G. W. Nb2O5 Supported on Mixed Oxides Catalyzed Oxidative and Photochemical Conversion of Anilines to Azoxybenzenes. New J. Chem. 2019, 43, 5863–5871. 10.1039/C9NJ00625G. [DOI] [Google Scholar]
  119. Mittal N.; Nisola G. M.; Chung W.-J. Facile Catalytic Dehydration of Fructose to 5-Hydroxymethylfurfural by Niobium Pentachloride. Tetrahedron Lett. 2012, 53, 3149–3155. 10.1016/j.tetlet.2012.04.045. [DOI] [Google Scholar]
  120. Zhang H. L.; Wu Q.; Guo C.; Wu Y.; Wu T. H. Photocatalytic Selective Oxidation of 5-Hydroxymethylfurfural to 2,5-Diformylfuran over Nb2O5 under Visible Light. ACS Sustain. Chem. Eng. 2017, 5, 3517–3523. 10.1021/acssuschemeng.7b00231. [DOI] [Google Scholar]
  121. Wang Y.; Kong X.; Jiang M.; Zhang F.; Lei X. A Z-Scheme ZnIn2S4/Nb2O5 Nanocomposite: Constructed and Used as An Efficient Bifunctional Photocatalyst for H2 Evolution and Oxidation of 5-Hydroxymethylfurfural. Inorg. Chem. Front. 2020, 7, 437–446. 10.1039/C9QI01196J. [DOI] [Google Scholar]
  122. Amadio E.; González-Fabra J.; Carraro D.; Denis W.; Gjoka B.; Zonta C.; Bartik K.; Cavani F.; Solmi S.; Bo C.; Licini G. Efficient Vanadium-Catalyzed Aerobic C–C Bond Oxidative Cleavage of Vicinal Diols. Adv. Synth. Catal. 2018, 360, 3286–3296. 10.1002/adsc.201800050. [DOI] [Google Scholar]
  123. Bordes-Richard E. Application of Concepts in Heterogeneous Oxidation of Hydrocarbons: Mo, V-Based Oxide Catalysts for Oxidation of Ethane and of N- And I-Butanes. Catal. Today 2021, 363, 15–26. 10.1016/j.cattod.2019.11.024. [DOI] [Google Scholar]
  124. Molinari J. E.; Wachs I. E. Presence of Surface Vanadium Peroxo-Oxo Umbrella Structures in Supported Vanadium Oxide Catalysts: Fact or Fiction?. J. Am. Chem. Soc. 2010, 132, 12559–12561. 10.1021/ja105392g. [DOI] [PubMed] [Google Scholar]
  125. Yalcin O.; Molinari Erwin J. E.; Gerceker D.; Onal I.; Wachs I. E. Role of Local Structure on Catalytic Reactivity: Comparison of Methanol Oxidation by Aqueous Bioinorganic Enzyme Mimic (Vanadium Haloperoxidase) and Vanadia-Based Heterogeneous Catalyst (Supported VO4/SiO2). ACS Catal. 2020, 10, 1566–1574. 10.1021/acscatal.9b02450. [DOI] [Google Scholar]
  126. Kortewille B.; Wachs I. E.; Cibura N.; Pfingsten O.; Bacher G.; Muhler M.; Strunk J. Photocatalytic Methanol Oxidation by Supported Vanadium Oxide Species: Influence of Support and Degree of Oligomerization. Eur. J. Inorg. Chem. 2018, 2018, 3725–3735. 10.1002/ejic.201800490. [DOI] [Google Scholar]
  127. Zhang N.; Xue C.; Wang K.; Fang Z. Efficient Oxidative Degradation of Fluconazole by A Heterogeneous Fenton Process with Cu-V Bimetallic Catalysts. Chem. Eng. J. 2020, 380, 122516. 10.1016/j.cej.2019.122516. [DOI] [Google Scholar]
  128. Miceli C.; Rintjema J.; Martin E.; Escudero-Adán E. C.; Zonta C.; Licini G.; Kleij A. W. Vanadium(V) Catalysts with High Activity for the Coupling of Epoxides and CO2: Characterization of a Putative Catalytic Intermediate. ACS Catal. 2017, 7, 2367–2373. 10.1021/acscatal.7b00109. [DOI] [Google Scholar]
  129. Son S.; Toste F. D. Non-Oxidative Vanadium-Catalyzed C-O Bond Cleavage: Application to Degradation of Lignin Model Compounds. Angew. Chem., Int. Ed. 2010, 49, 3791–3794. 10.1002/anie.201001293. [DOI] [PMC free article] [PubMed] [Google Scholar]
  130. Sedai B.; Díaz-Urrutia C.; Baker R. T.; Wu R.; Silks L. A. P.; Hanson S. K. Comparison of Copper and Vanadium Homogeneous Catalysts for Aerobic Oxidation of Lignin Models. ACS Catal. 2011, 1, 794–804. 10.1021/cs200149v. [DOI] [Google Scholar]
  131. Hanson S. K.; Wu R.; Silks L. A. C-C or C-O Bond Cleavage in A Phenolic Lignin Model Compound: Selectivity Depends on Vanadium Catalyst. Angew. Chem., Int. Ed. 2012, 51, 3410–3413. 10.1002/anie.201107020. [DOI] [PubMed] [Google Scholar]
  132. Sedai B.; Díaz-Urrutia C.; Baker R. T.; Wu R.; Silks L. A. P.; Hanson S. K. Aerobic Oxidation of β-1 Lignin Model Compounds with Copper and Oxovanadium Catalysts. ACS Catal. 2013, 3, 3111–3122. 10.1021/cs400636k. [DOI] [Google Scholar]
  133. Díaz-Urrutia C.; Sedai B.; Leckett K. C.; Baker R. T.; Hanson S. K. Aerobic Oxidation of 2-Phenoxyethanol Lignin Model Compounds Using Vanadium and Copper Catalysts. ACS Sustainable Chem. Eng. 2016, 4, 6244–6251. 10.1021/acssuschemeng.6b02420. [DOI] [Google Scholar]
  134. Jiang Y.-Y.; Yan L.; Yu H.-Z.; Zhang Q.; Fu Y. Mechanism of Vanadium-Catalyzed Selective C-O and C-C Cleavage of Lignin Model Compound. ACS Catal. 2016, 6, 4399–4410. 10.1021/acscatal.6b00239. [DOI] [Google Scholar]
  135. Mottweiler J.; Puche M.; Rauber C.; Schmidt T.; Concepcion P.; Corma A.; Bolm C. Copper- and Vanadium-Catalyzed Oxidative Cleavage of Lignin using Dioxygen. ChemSusChem 2015, 8, 2106–2113. 10.1002/cssc.201500131. [DOI] [PubMed] [Google Scholar]
  136. Liu H.; Li H.; Luo N.; Wang F. Visible-Light-Induced Oxidative Lignin C-C Bond Cleavage to Aldehydes Using Vanadium Catalysts. ACS Catal. 2020, 10, 632–643. 10.1021/acscatal.9b03768. [DOI] [Google Scholar]
  137. Kataoka Y.; Takai K.; Oshima K.; Utimoto K. Reduction of Acetylenes to (Z)-Olefins by Means of Low-Valent Niobium or Tantalum. Tetrahedron Lett. 1990, 31, 365–368. 10.1016/S0040-4039(00)94556-8. [DOI] [Google Scholar]
  138. Kataoka Y.; Miyai J.; Oshima K.; Takai K.; Utimoto K. Reactions between Tantalum Alkyne or Niobium Alkyne Complexes and Carbonyl-Compounds. J. Org. Chem. 1992, 57, 1973–1981. 10.1021/jo00033a015. [DOI] [Google Scholar]
  139. Oh K.; Knabe W. E. Lewis Acid-Promoted Electron Transfer Deoxygenation of Epoxides, Sulfoxides, and Amine N-Oxides: The Role of Low-Valent Niobium Complexes from NbCl5 and Zn. Tetrahedron 2009, 65, 2966–2974. 10.1016/j.tet.2009.02.013. [DOI] [Google Scholar]
  140. Shen L.; Xia Y.; Lin S.; Liang S.; Wu L. An Unsaturated Metal Site-Promoted Approach to Construct Strongly Coupled Noble Metal/HNb3O8 Nanosheets For Efficient Thermo/Photo-Catalytic Reduction. Nanoscale 2017, 9, 14654–14663. 10.1039/C7NR05288J. [DOI] [PubMed] [Google Scholar]
  141. da Silva G. T. S. T.; Nogueira A. E.; Oliveira J. A.; Torres J. A.; Lopes O. F.; Ribeiro C. Acidic Surface Niobium Pentoxide Is Catalytic Active for CO2 Photoreduction. Appl. Catal., B 2019, 242, 349–357. 10.1016/j.apcatb.2018.10.017. [DOI] [Google Scholar]
  142. Jiao X.; Zheng K.; Chen Q.; Li X.; Li Y.; Shao W.; Xu J.; Zhu J.; Pan Y.; Sun Y.; Xie Y. Photocatalytic Conversion of Waste Plastics into C2 Fuels under Simulated Natural Environment Conditions. Angew. Chem., Int. Ed. 2020, 59, 15497–15501. 10.1002/anie.201915766. [DOI] [PubMed] [Google Scholar]
  143. Sudo Y.; Arai S.; Nishida A. Facile and Regioselective Dealkylation of Alkyl Aryl Ethers Using Niobium(V) Pentachloride. Eur. J. Org. Chem. 2006, 2006, 752–758. 10.1002/ejoc.200500502. [DOI] [Google Scholar]
  144. Roskamp E. J.; Pedersen S. F. The First Practical Niobium(III) Reagent in Organic Synthesis. A Convenient Route to 2-Amino Alcohols via The Coupling of Imines with Aldehydes or Ketones Promoted by NbCl3(DME). J. Am. Chem. Soc. 1987, 109, 6551–6553. 10.1021/ja00255a073. [DOI] [Google Scholar]
  145. Shimizu H.; Kobayashi S. Convenient Synthesis of α-Amino Amides using Low-Valent Tantalum Prepared from TaCl5 and Zn. Tetrahedron Lett. 2005, 46, 7593–7595. 10.1016/j.tetlet.2005.08.131. [DOI] [Google Scholar]
  146. Clerici M. G.; Maspero F. Catalytic C-Alkylation of Secondary Amines with Alkenes. Synthesis 1980, 1980, 305–306. 10.1055/s-1980-29002. [DOI] [Google Scholar]
  147. Nugent W. A.; Ovenall D. W.; Holmes S. J. Catalytic C-H Activation in Early Transition-Metal Dialkylamides and Alkoxides. Organometallics 1983, 2, 161–162. 10.1021/om00073a031. [DOI] [Google Scholar]
  148. Herzon S. B.; Hartwig J. F. Direct, Catalytic Hydroaminoalkylation of Unactivated Olefins with N-Alkyl Arylamines. J. Am. Chem. Soc. 2007, 129, 6690–6691. 10.1021/ja0718366. [DOI] [PMC free article] [PubMed] [Google Scholar]
  149. Herzon S. B.; Hartwig J. F. Hydroaminoalkylation of Unactivated Olefins with Dialkylamines. J. Am. Chem. Soc. 2008, 130, 14940–14941. 10.1021/ja806367e. [DOI] [PMC free article] [PubMed] [Google Scholar]
  150. Reznichenko A. L.; Emge T. J.; Audörsch S.; Klauber E. G.; Hultzsch K. C.; Schmidt B. Group 5 Metal Binaphtholate Complexes for Catalytic Asymmetric Hydroaminoalkylation and Hydroamination/Cyclization. Organometallics 2011, 30, 921–924. 10.1021/om1011006. [DOI] [Google Scholar]
  151. Reznichenko A. L.; Hultzsch K. C. The Mechanism of Hydroaminoalkylation Catalyzed by Group 5 Metal Binaphtholate Complexes. J. Am. Chem. Soc. 2012, 134, 3300–3311. 10.1021/ja211945m. [DOI] [PubMed] [Google Scholar]
  152. Chong E.; Brandt J. W.; Schafer L. L. 2-Pyridonate tantalum Complexes for The Intermolecular Hydroaminoalkylation of Sterically Demanding Alkenes. J. Am. Chem. Soc. 2014, 136, 10898–10901. 10.1021/ja506187m. [DOI] [PubMed] [Google Scholar]
  153. Lauzon J. M.; Eisenberger P.; Roşca S.-C.; Schafer L. L. Amidate Complexes of Tantalum and Niobium for The Hydroaminoalkylation of Unactivated Alkenes. ACS Catal. 2017, 7, 5921–5931. 10.1021/acscatal.7b01293. [DOI] [Google Scholar]
  154. Edwards P. M.; Schafer L. L. In Situ Generation of a Regio- and Diastereoselective Hydroaminoalkylation Catalyst using Commercially Available Starting Materials. Org. Lett. 2017, 19, 5720–5723. 10.1021/acs.orglett.7b02149. [DOI] [PubMed] [Google Scholar]
  155. Brandt J. W.; Chong E.; Schafer L. L. Ligand Effects and Kinetic Investigations of Sterically Accessible 2-Pyridonate Tantalum Complexes for Hydroaminoalkylation. ACS Catal. 2017, 7, 6323–6330. 10.1021/acscatal.7b01486. [DOI] [Google Scholar]
  156. Gilmour D. J.; Lauzon J. M. P.; Clot E.; Schafer L. L. Ta-Catalyzed Hydroaminoalkylation of Alkenes: Insights into Ligand-Modified Reactivity using DFT. Organometallics 2018, 37, 4387–4394. 10.1021/acs.organomet.8b00674. [DOI] [Google Scholar]
  157. Garcia P.; Lau Y. Y.; Perry M. R.; Schafer L. L. Phosphoramidate Tantalum Complexes for Room-Temperature C-H Functionalization: Hydroaminoalkylation Catalysis. Angew. Chem., Int. Ed. 2013, 52, 9144–9148. 10.1002/anie.201304153. [DOI] [PubMed] [Google Scholar]
  158. Edwards P. M.; Schafer L. L. Early Transition Metal-Catalyzed C-H Alkylation: Hydroaminoalkylation for Csp3-CSP3 Bond Formation in The Synthesis of Selectively Substituted Amines. Chem. Commun. 2018, 54, 12543–12560. 10.1039/C8CC06445H. [DOI] [PubMed] [Google Scholar]
  159. Zhang Z.; Hamel J.-D.; Schafer L. L. TaMe3Cl2-Catalyzed Intermolecular Hydroaminoalkylation: A Simple Complex for Enhanced Reactivity and Expanded Substrate Scope. Chem.—Eur. J. 2013, 19, 8751–8754. 10.1002/chem.201300992. [DOI] [PubMed] [Google Scholar]
  160. Daneshmand P.; Rosca S. C.; Dalhoff R.; Yin K.; DiPucchio R. C.; Ivanovich R. A.; Polat D. E.; Beauchemin A. M.; Schafer L. L. Cyclic Ureate Tantalum Catalyst for Preferential Hydroaminoalkylation with Aliphatic Amines: Mechanistic Insights into Substrate Controlled Reactivity. J. Am. Chem. Soc. 2020, 142, 15740–15750. 10.1021/jacs.0c04579. [DOI] [PubMed] [Google Scholar]
  161. DiPucchio R. C.; Lenzen K. E.; Daneshmand P.; Ezhova M. B.; Schafer L. L. Direct, Catalytic α-Alkylation of N-Heterocycles by Hydroaminoalkylation: Substrate Effects for Regiodivergent Product Formation. J. Am. Chem. Soc. 2021, 143, 11243–11250. 10.1021/jacs.1c05498. [DOI] [PubMed] [Google Scholar]
  162. Saadati F.; Griffin S. E.; Schafer L. L. Guanidinate Early-Transition-Metal Complexes: Efficient and Selective Hydroaminoalkylation of Alkenes. Organometallics 2022, 41, 1816. 10.1021/acs.organomet.2c00043. [DOI] [Google Scholar]
  163. DiPucchio R. C.; Rosca S.-C.; Schafer L. L. Hydroaminoalkylation for the Catalytic Addition of Amines to Alkenes or Alkynes: Diverse Mechanisms Enable Diverse Substrate Scope. J. Am. Chem. Soc. 2022, 144, 11459–11481. 10.1021/jacs.1c10397. [DOI] [PubMed] [Google Scholar]
  164. Lauzon J. M. P.; Schafer L. L. Tantallaaziridines: from synthesis to catalytic applications. Dalton Trans. 2012, 41, 11539–11550. 10.1039/c2dt30781b. [DOI] [PubMed] [Google Scholar]
  165. Chong E.; Garcia P.; Schafer L. L. Hydroaminoalkylation: Early-Transition-Metal-Catalyzed alpha-Alkylation of Amines. Synthesis-Stuttgart 2014, 46, 2884–2896. 10.1055/s-0034-1379216. [DOI] [Google Scholar]
  166. Li X.; Li X.; Jiao N. Rh-Catalyzed Construction of Quinolin-2(1H)-ones via C-H Bond Activation of Simple Anilines with CO and Alkynes. J. Am. Chem. Soc. 2015, 137, 9246–9249. 10.1021/jacs.5b05843. [DOI] [PubMed] [Google Scholar]
  167. O’Connor J. M.; Friese S. J.; Rodgers B. L. A Transition-Metal-Catalyzed Enediyne Cycloaromatization. J. Am. Chem. Soc. 2005, 127, 16342–16343. 10.1021/ja050060a. [DOI] [PubMed] [Google Scholar]
  168. Jia T.; Zhao C.; He R.; Chen H.; Wang C. Iron-Carbonyl-Catalyzed Redox-Neutral [4 + 2] Annulation of N-H Imines and Internal Alkynes by C-H Bond Activation. Angew. Chem., Int. Ed. 2016, 55, 5268–5271. 10.1002/anie.201600365. [DOI] [PubMed] [Google Scholar]
  169. Zhao Q.; Fu W. C.; Kwong F. Y. Palladium-Catalyzed Regioselective Aromatic Extension of Internal Alkynes through a Norbornene-Controlled Reaction Sequence. Angew. Chem., Int. Ed. 2018, 57, 3381–3385. 10.1002/anie.201713207. [DOI] [PubMed] [Google Scholar]
  170. Zhang G.; Lin Y.; Luo X.; Hu X.; Chen C.; Lei A. Oxidative [4 + 2] Annulation of Styrenes with Alkynes under External-Oxidant-Free Conditions. Nat. Commun. 2018, 9, 1225. 10.1038/s41467-018-03534-z. [DOI] [PMC free article] [PubMed] [Google Scholar]
  171. Lu Q.; Gressies S.; Cembellin S.; Klauck F. J. R.; Daniliuc C. G.; Glorius F. Redox-Neutral Manganese(I)-Catalyzed C-H Activation: Traceless Directing Group Enabled Regioselective Annulation. Angew. Chem., Int. Ed. 2017, 56, 12778–12782. 10.1002/anie.201707396. [DOI] [PubMed] [Google Scholar]
  172. Sagadevan A.; Ragupathi A.; Hwang K. C. Photoinduced Copper-Catalyzed Regioselective Synthesis of Indoles: Three-Component Coupling of Arylamines, Terminal Alkynes, and Quinones. Angew. Chem., Int. Ed. 2015, 54, 13896–13901. 10.1002/anie.201506579. [DOI] [PubMed] [Google Scholar]
  173. Hartung J. B.; Pedersen S. F. A Regioselective Synthesis of 2,3-Disubstituted-1-Naphthols. The Coupling of Alkynes with 1,2-Aryldialdehydes Promoted by NbCl3(DME). J. Am. Chem. Soc. 1989, 111, 5468–5469. 10.1021/ja00196a064. [DOI] [Google Scholar]
  174. Roskamp E. J.; Dragovich P. S.; Hartung J. B.; Pedersen S. F. A Regioselective Synthesis of Pyrroles via The Coupling of α,β-Unsaturated Imines with Esters or N,N-Dimethylformamide Promoted by NbCl3(DME). J. Org. Chem. 1989, 54, 4736–4737. 10.1021/jo00281a006. [DOI] [Google Scholar]
  175. Kataoka Y.; Miyai J.; Tezuka M.; Takai K.; Oshima K.; Utimoto K. Preparation of 1-Naphthols from Acetylenes and O-Phthalaldehyde using Low-Valent Tantalum and Niobium. Tetrahedron Lett. 1990, 31, 369–372. 10.1016/S0040-4039(00)94557-X. [DOI] [Google Scholar]
  176. Du Plessis J. A. K.; Viljoen J. S.; Du Toit C. J. The Co-Cyclotrimerization of Hexynes and Phenylacetylene with Niobium(V) Chloride as Catalyst. J. Mol. Catal. 1991, 64, 269–275. 10.1016/0304-5102(91)85136-P. [DOI] [Google Scholar]
  177. Takai K.; Yamada M.; Utimoto K. Selective Cyclotrimerization of Acetylenes via Tantalum-Alkyne Complexes. Chem. Lett. 1995, 24, 851–852. 10.1246/cl.1995.851. [DOI] [Google Scholar]
  178. Oshiki T.; Nomoto H.; Tanaka K.; Takai K. Catalytic Performance of Tantalum−η2-Alkyne Complexes [TaCl3(R1C≡CR2)L2] for Alkyne Cyclotrimerization. Bull. Chem. Soc. Jpn. 2004, 77, 1009–1011. 10.1246/bcsj.77.1009. [DOI] [Google Scholar]
  179. Obora Y.; Takeshita K.; Ishii Y. NbCl3-Catalyzed [2 + 2+2] Intermolecular Cycloaddition of Alkynes and Alkenes to 1,3-Cyclohexadiene Derivatives. Org. Biomol. Chem. 2009, 7, 428–431. 10.1039/B820352K. [DOI] [PubMed] [Google Scholar]
  180. Obora Y.; Satoh Y.; Ishii Y. NbCl3-Catalyzed Intermolecular [2 + 2+2] Cycloaddition of Alkynes and α,ω-Dienes: Highly Chemo- and Regioselective Formation of 5-ω-Alkenyl-1,4-Substituted-1,3-Cyclohexadiene Derivatives. J. Org. Chem. 2010, 75, 6046–6049. 10.1021/jo101229u. [DOI] [PubMed] [Google Scholar]
  181. Satoh Y.; Obora Y. NbCl3-Catalyzed Three-Component [2 + 2+2] Cycloaddition Reaction of Terminal Alkynes, Internal Alkynes, and Alkenes to 1,3,4,5-Tetrasubstituted 1,3-Cyclohexadienes. Org. Lett. 2011, 13, 2568–2571. 10.1021/ol200662e. [DOI] [PubMed] [Google Scholar]
  182. Satoh Y.; Obora Y. Active Low-Valent Niobium Catalysts from NbCl5 and Hydrosilanes for Selective Intermolecular Cycloadditions. J. Org. Chem. 2011, 76, 8569–8573. 10.1021/jo201757w. [DOI] [PubMed] [Google Scholar]
  183. Kamei M.; Watanabe K.; Fuji M.; Obora Y. Selective Intermolecular [2 + 2+2] Cycloaddition of Terminal Alkynes and Alkenes by NbCl5 as a Catalyst Precursor. Chem. Lett. 2016, 45, 943–945. 10.1246/cl.160481. [DOI] [Google Scholar]
  184. Satoh Y.; Obora Y. Niobium Complexes in Organic Transformations: from Stoichiometric Reactions to Catalytic [2 + 2+2] Cycloaddition Reactions. Eur. J. Org. Chem. 2015, 2015, 5041–5054. 10.1002/ejoc.201500358. [DOI] [Google Scholar]
  185. Satoh Y.; Yasuda K.; Obora Y. Strategy for The Synthesis of Pyrimidine Derivatives: NbCl5-Mediated Cycloaddition of Alkynes and Nitriles. Organometallics 2012, 31, 5235–5238. 10.1021/om300669s. [DOI] [Google Scholar]
  186. Satoh Y.; Obora Y. Low-Valent Niobium-Catalyzed Intermolecular [2 + 2+2] Cycloaddition of Tert-Butylacetylene and Arylnitriles to Form 2,3,6-Trisubstituted Pyridine Derivatives. J. Org. Chem. 2013, 78, 7771–7776. 10.1021/jo401399y. [DOI] [PubMed] [Google Scholar]
  187. Ozaki M.; Obora Y.; Tada Y.; Ishii Y. Generation of Low-Valent Alkoxy Niobium from Nb(OEt)5 and Grignard Reagents and Their Use as Catalysts in The Cyclotrimerization of Isocyanates. J. Organomet. Chem. 2013, 741–742, 109–113. 10.1016/j.jorganchem.2013.05.035. [DOI] [Google Scholar]
  188. Watanabe K.; Satoh Y.; Kamei M.; Furukawa H.; Fuji M.; Obora Y. NbCl5/Zn/PCy3-System-Catalyzed Intramolecular [2 + 2 + 2] Cycloadditions of Diynes and Alkenes to Form Bicyclic Cyclohexadienes. Org. Lett. 2017, 19, 5398–5401. 10.1021/acs.orglett.7b02672. [DOI] [PubMed] [Google Scholar]
  189. Fuji M.; Obora Y. FeCl3-Assisted Niobium-Catalyzed Cycloaddition of Nitriles and Alkynes: Synthesis of Alkyl- and Arylpyrimidines Based on Independent Functions of NbCl5 and FeCl3 Lewis Acids. Org. Lett. 2017, 19, 5569–5572. 10.1021/acs.orglett.7b02708. [DOI] [PubMed] [Google Scholar]
  190. Wu Z.; Zhang J.; Su Z.; Lu S.; Huang J.; Liang Y.; Tan T.; Xiao F.-S. Selective Conversion of Acetone to Mesitylene over Tantalum Phosphate Catalysts. Chem. Commun. 2022, 58, 2862–2865. 10.1039/D2CC00016D. [DOI] [PubMed] [Google Scholar]
  191. Nakajima K.; Baba Y.; Noma R.; Kitano M.; Kondo J. N.; Hayashi S.; Hara M. Nb2O5.nH2O as A Heterogeneous Catalyst with Water-Tolerant Lewis Acid Sites. J. Am. Chem. Soc. 2011, 133, 4224–4227. 10.1021/ja110482r. [DOI] [PubMed] [Google Scholar]
  192. Makio H.; Terao H.; Iwashita A.; Fujita T. FI Catalysts for Olefin Polymerization-A Comprehensive Treatment. Chem. Rev. 2011, 111, 2363–2449. 10.1021/cr100294r. [DOI] [PubMed] [Google Scholar]
  193. Toda T.; Nakata N.; Matsuo T.; Ishii A. Synthesis, Structure, and 1-Hexene Polymerization Catalytic Ability of Group 5 Metal Complexes Incorporating an [OSSO]-Type Ligand. ACS Catal. 2013, 3, 1764–1767. 10.1021/cs4003996. [DOI] [Google Scholar]
  194. Zhang S. W.; Lu L. P.; Long Y. Y.; Li Y. S. Ethylene Polymerization and Ethylene/Hexene Copolymerization by Vanadium(III) Complexes Bearing Bidentate Phenoxy-Phosphine Oxide Ligands. J. Polym. Sci. A Polym. Chem. 2013, 51, 5298–5306. 10.1002/pola.26963. [DOI] [Google Scholar]
  195. Zhang S.; Zhang W. C.; Shang D. D.; Zhang Z. Q.; Wu Y. X. Ethylene/Propylene Copolymerization Catalyzed by Vanadium Complexes Containing N-Heterocyclic Carbenes. Dalton Trans. 2015, 44, 15264–15270. 10.1039/C5DT00675A. [DOI] [PubMed] [Google Scholar]
  196. Białek M.; Bisz E. Dichlorovanadium(IV) Diamine-Bis(Phenolate) Complexes for Ethylene (Co)Polymerization and 1-Olefin Isospecific Polymerization. J. Catal. 2018, 362, 65–73. 10.1016/j.jcat.2018.03.029. [DOI] [Google Scholar]
  197. Hou X.; Nomura K. Arylimido)Vanadium(V)-Alkylidene Complexes Containing Fluorinated Aryloxo and Alkoxo Ligands for Fast Living Ring-Opening Metathesis Polymerization (ROMP) and Highly Cis-Specific ROMP. J. Am. Chem. Soc. 2015, 137, 4662–4665. 10.1021/jacs.5b02149. [DOI] [PubMed] [Google Scholar]
  198. Hou X.; Nomura K. Ring-Opening Metathesis Polymerization of Cyclic Olefins by (Arylimido)vanadium(V)-Alkylidenes: Highly Active, Thermally Robust Cis Specific Polymerization. J. Am. Chem. Soc. 2016, 138, 11840–11849. 10.1021/jacs.6b06330. [DOI] [PubMed] [Google Scholar]
  199. Sueyoshi S.; Taniguchi T.; Tanaka S.; Asakawa H.; Nishimura T.; Maeda K. Understanding the Polymerization of Diphenylacetylenes with Tantalum(V) Chloride and Cocatalysts: Production of Cyclic Poly(diphenylacetylene)s by Low-Valent Tantalum Species Generated in Situ. J. Am. Chem. Soc. 2021, 143, 16136–16146. 10.1021/jacs.1c06811. [DOI] [PubMed] [Google Scholar]
  200. Constable D. J. C.; Dunn P. J.; Hayler J. D.; Humphrey G. R.; Leazer J. J. L.; Linderman R. J.; Lorenz K.; Manley J.; Pearlman B. A.; Wells A.; Zaks A.; Zhang T. Y. Key Green Chemistry Research Areas-A Perspective From Pharmaceutical Manufacturers. Green Chem. 2007, 9, 411–420. 10.1039/B703488C. [DOI] [Google Scholar]
  201. Pattabiraman V. R.; Bode J. W. Rethinking Amide Bond Synthesis. Nature 2011, 480, 471–479. 10.1038/nature10702. [DOI] [PubMed] [Google Scholar]
  202. Allen C. L.; Williams J. M. Metal-Catalysed Approaches to Amide Bond Formation. Chem. Soc. Rev. 2011, 40, 3405–3415. 10.1039/c0cs00196a. [DOI] [PubMed] [Google Scholar]
  203. Lundberg H.; Tinnis F.; Selander N.; Adolfsson H. Catalytic Amide Formation from Non-Activated Carboxylic Acids and Amines. Chem. Soc. Rev. 2014, 43, 2714–2742. 10.1039/C3CS60345H. [DOI] [PubMed] [Google Scholar]
  204. de Figueiredo R. M.; Suppo J. S.; Campagne J. M. Nonclassical Routes for Amide Bond Formation. Chem. Rev. 2016, 116, 12029–12122. 10.1021/acs.chemrev.6b00237. [DOI] [PubMed] [Google Scholar]
  205. Noda H.; Furutachi M.; Asada Y.; Shibasaki M.; Kumagai N. Unique Physicochemical and Catalytic Properties Dictated by The B3NO2 Ring System. Nat. Chem. 2017, 9, 571–577. 10.1038/nchem.2708. [DOI] [PubMed] [Google Scholar]
  206. Sabatini M. T.; Boulton L. T.; Sneddon H. F.; Sheppard T. D. A Green Chemistry Perspective on Catalytic Amide Bond Formation. Nat. Catal. 2019, 2, 10–17. 10.1038/s41929-018-0211-5. [DOI] [Google Scholar]
  207. Tsuji H.; Yamamoto H. Hydroxy-Directed Amidation of Carboxylic Acid Esters using A Tantalum Alkoxide Catalyst. J. Am. Chem. Soc. 2016, 138, 14218–14221. 10.1021/jacs.6b09482. [DOI] [PubMed] [Google Scholar]
  208. Muramatsu W.; Tsuji H.; Yamamoto H. Catalytic Peptide Synthesis: Amidation of N-Hydroxyimino Esters. ACS Catal. 2018, 8, 2181–2187. 10.1021/acscatal.7b04244. [DOI] [Google Scholar]
  209. Muramatsu W.; Hattori T.; Yamamoto H. Substrate-Directed Lewis-Acid Catalysis for Peptide Synthesis. J. Am. Chem. Soc. 2019, 141, 12288–12295. 10.1021/jacs.9b03850. [DOI] [PubMed] [Google Scholar]
  210. Muramatsu W.; Yamamoto H. Tantalum-Catalyzed Amidation of Amino Acid Homologues. J. Am. Chem. Soc. 2019, 141, 18926–18931. 10.1021/jacs.9b08415. [DOI] [PubMed] [Google Scholar]
  211. Zhang P.; Zhang J.; Gong J. Tantalum-Based Semiconductors for Solar Water Splitting. Chem. Soc. Rev. 2014, 43, 4395–4422. 10.1039/C3CS60438A. [DOI] [PubMed] [Google Scholar]
  212. Ahmed M.; Xinxin G. A Review of Metal Oxynitrides for Photocatalysis. Inorg. Chem. Front. 2016, 3, 578–590. 10.1039/C5QI00202H. [DOI] [Google Scholar]
  213. Hitoki G.; Takata T.; Kondo J. N.; Hara M.; Kobayashi H.; Domen K. An Oxynitride, TaON, as An Efficient Water Oxidation Photocatalyst under Visible Light Irradiation (λ ≤ 500 nm). Chem. Commun. 2002, 2002, 1698–1699. 10.1039/B202393H. [DOI] [PubMed] [Google Scholar]
  214. Nakamura R.; Tanaka T.; Nakato Y. Oxygen Photoevolution on A Tantalum Oxynitride Photocatalyst under Visible-Light Irradiation: How Does Water Photooxidation Proceed on A Metal-Oxynitride Surface?. J. Phys. Chem. B 2005, 109, 8920–8927. 10.1021/jp0501289. [DOI] [PubMed] [Google Scholar]
  215. Hitoki G.; Ishikawa A.; Takata T.; Kondo J. N.; Hara M.; Domen K. Ta3N5 as A Novel Visible Light-Driven Photocatalyst (λ < 600 nm). Chem. Lett. 2002, 31, 736–737. 10.1246/cl.2002.736. [DOI] [Google Scholar]
  216. Maeda K.; Higashi M.; Lu D. L.; Abe R.; Domen K. Efficient Nonsacrificial Water Splitting through Two-Step Photoexcitation by Visible Light using a Modified Oxynitride as a Hydrogen Evolution Photocatalyst. J. Am. Chem. Soc. 2010, 132, 5858–5868. 10.1021/ja1009025. [DOI] [PubMed] [Google Scholar]
  217. Maeda K.; Terashima H.; Kase K.; Higashi M.; Tabata M.; Domen K. Surface Modification of TaON with Monoclinic ZrO2 to Produce a Composite Photocatalyst with Enhanced Hydrogen Evolution Activity under Visible Light. Bull. Chem. Soc. Jpn. 2008, 81, 927–937. 10.1246/bcsj.81.927. [DOI] [Google Scholar]
  218. Maeda K.; Lu D.; Domen K. Direct Water Splitting into Hydrogen and Oxygen under Visible Light by using Modified TaON Photocatalysts with d0 Electronic Configuration. Chem.—Eur. J. 2013, 19, 4986–4991. 10.1002/chem.201300158. [DOI] [PubMed] [Google Scholar]

Associated Data

This section collects any data citations, data availability statements, or supplementary materials included in this article.

Data Availability Statement

The data underlying this study are available in the published article.

Articles from ACS Organic & Inorganic Au are provided here courtesy of American Chemical Society

RESOURCES