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. 2023 Jan 4;25(1):120–124. doi: 10.1021/acs.orglett.2c03916

Iron-Catalyzed Cross-Coupling of α-Allenyl Esters with Grignard Reagents for the Synthesis of 1,3-Dienes

Wei-Jun Kong 1,*, Simon N Kessler 1, Haibo Wu 1, Jan-E Bäckvall 1,*
PMCID: PMC9841610  PMID: 36599130

Abstract

graphic file with name ol2c03916_0007.jpg

Structurally diverse 1,3-dienes are valuable building blocks in organic synthesis. Herein we report the iron-catalyzed coupling between α-allenyl esters and Grignard reagents, which provides a fast and practical approach to a variety of complex substituted 1,3-dienes. The reaction involves an inexpensive iron catalyst, mild reaction conditions, and provides easy scale up.

1,3-Dienes are important structural motifs in natural products and valuable building blocks in organic synthesis.1 A plethora of transformations involving 1,3-dienes have been developed including Diels–Alder addition,2 hydrofunctionalization,3 and difunctionalization.4 Traditionally, olefination reactions such as Wittig, Horner–Wadsworth–Emmons, and Julia–Kocienski reactions are applied for the synthesis of 1,3-dienes.5 However, these methods sometimes suffer from the drawbacks of low atom economy, poor functional group tolerance, or unsatisfactory stereoselectivity. Methodologies providing simple and efficient access to structurally diverse substituted 1,3-dienes are still in high demand.

In recent years, transition metal catalysis has become a powerful tool for the synthesis of 1,3-dienes through reactions including Mizoroki–Heck reactions, cross-coupling, ene-yne metathesis, isomerization, and so on (Scheme 1A).6 The control of regio- and stereoselectivity still constitutes the main challenge in these transition metal-catalyzed 1,3-diene synthesis reactions. While palladium catalysts play a major role in these reactions, methods based on inexpensive 3d metal catalysts, such as iron,7 copper,8 and nickel,9 are still underdeveloped. Iron catalysis has received considerable attention in organic chemistry due to its high earth abundance and low toxicity. Notable reactions catalyzed by iron complexes include cross couplings,10 oxidations,11 and C–H functionalizations,12 among others.

Scheme 1. Previous Work on Transition Metal-Catalyzed 1,3-Diene Synthesis (A) and This Work (B).

Scheme 1

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α-Allenyl esters or carbonates have been explored in palladium- and iridium-catalyzed asymmetric nucleophilic substitution (SN) reaction for chiral allene synthesis.13 Furthermore, they were also found to be valuable reagents for 1,3-diene synthesis as demonstrated in palladium-, rhodium-, and cobalt-catalyzed coupling reactions (Scheme 1A, lower part to the right).14 However, most of these reactions are limited to sterically unhindered α-allenyl derivatives, such as terminal allenes. In previous studies, our group has demonstrated the versatility of iron catalysis in allene synthesis with propargylic esters and ethers as substrates via an SN2′ pathway.15 Therefore, it is conceivable that 1,3-dienes could be accessed from α-allenyl derivatives through an iron-catalyzed reaction. Herein, we report a mild and efficient approach for the regio- and stereoselective synthesis of 1,3-dienes from structurally diverse α-allenyl esters using iron catalysis (Scheme 1B).

We initiated the envisaged iron-catalyzed reaction with α-allenic acetates 1a (R = OAc) and benzyl magnesium chloride 2a as starting materials. The desired 1,3-diene 3aa was obtained in 93% NMR yield with an E/Z ratio of 7.5:1 using 5.0 mol % of tris(acetylacetonate)iron (Fe(acac)3) as precatalyst and diethyl ether (Et2O) as solvent at −20 °C for 20 min (Table 1, entry 1). On isolation with column chromatography on silica (92% yield) the E/Z ratio decreased to 5.0:1. When ferric chloride (FeCl3) was used as catalyst, a similar result was obtained with a slight decrease in yield (85%, Table 1, entry 2). However, ferrous chloride (FeCl2) only afforded 3aa in 16% yield (entry 3). Solvents such as toluene or tetrahydrofuran (THF) also delivered 3aa in excellent yields, but the stereoselectivity was unsatisfactory with E/Z ratios of 3.9:1 and 2.5:1, respectively (entry 4 and 5). When methoxide was used as leaving group, the reaction delivered 3aa in only 36% yield with an E/Z ratio of 17:1 (entry 6). The use of pivalate 1a (R = Piv) afforded the diene product in 85% yield with an E/Z ratio of 4.7:1. The reaction of acetate 1a (R = Ac) at elevated temperature (0 °C) gave a similar result (92% yield and E/Z = 7.5:1) as that at −20 °C (entry 8 vs entry 1, Table 1). The addition of catalytic amounts of tetramethylethylenediamine (TMEDA) improved the yield to 96%, but the E/Z ratio decreased to 3.5:1 (entry 9, Table 1). A control experiment proved the indispensability of the iron catalyst in this reaction (entry 10, Table 1). To rule out the possibility that the reactivity was due to trace amounts of impurities such as palladium or copper in the iron precatalyst, we ran the reaction with the amounts of Pd(OAc)2 or CuI that would correspond to 0.1 wt % of the Fe(acac)3 (5 mol %) used. In both cases <5% of product 3aa was formed (entry 11, Table 1).

Table 1. Optimization of Iron-Catalyzed 1,3-Diene Synthesis from α-Allenyl Derivativesa.

graphic file with name ol2c03916_0006.jpg

entry R [Fe] solvent 3aa (%) E/Z
1 Ac Fe(acac)3 Et2O 93(92)b 7.5:1(5.0:1)c
2 Ac FeCl3 Et2O 85 7.5:1
3 Ac FeCl2 Et2O 16 4.3:1
4 Ac Fe(acac)3 toluene 94 3.9:1
5 Ac Fe(acac)3 THF 90 2.2:1
6 Me Fe(acac)3 Et2O 36 17:1
7 Piv Fe(acac)3 Et2O 85 4.7:1
8d Ac Fe(acac)3 Et2O 92 7.5:1
9e Ac Fe(acac)3 Et2O 96 3.5:1
10f Ac – Et2O <5 –
11g Ac – Et2O <5 –
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a

Reaction conditions: 1a (0.2 mmol), 2a (0.25 mmol), Fe catalyst (5.0 mol %), solvent (1.0 mL), −20 °C, 20 min. Yields and E/Z ratios were determined by 1H NMR analysis of crude mixture with CH2Br2 as internal standards.

b

Isolated yield in parentheses.

c

E/Z ratio after isolation via chromatography in parentheses.

d

0 °C.

e

10 mol % of tetramethylethylenediamine (TMEDA) was added.

f

No iron catalyst was added.

g

Run with Pd(OAc)2 or CuI that would correspond to 0.1 wt % of the Fe(acac)3 (5 mol %) used.

We first explored the scope of α-allenyl acetates (Scheme 2). The α-phenyl-allenyl acetate (1b) gave the desired product 3ba in 84% yield and excellent stereoselectivity (E/Z = 14:1). With the electron withdrawing p-chlorophenyl in the α-position (1c), the corresponding 1,3-diene was obtained in 92% yield (E/Z = 4.9:1). α-Allenyl acetate 1d bearing a m-methoxyphenyl group in the α-position gave 3da in 92% yield with a moderate E/Z ratio (4.1:1). α-Naphthyl-allenyl acetate (1e) was also a suitable substrate, which afforded 1,3-diene 3ea in an almost quantitative yield with an E/Z ratio of 7.3:1. The unsubstituted α-allenyl acetate 1f delivered 2-benzyl-1,3-butadiene (3fa) in 72% yield in 1.0 mmol scale. α-(n-Pentyl) substituted α-allenyl acetate was also a feasible substrate (1g), providing 3ga in 84% yield and E/Z = 4.9:1. Trisubstituted allenic acetates with R1 = Me, R2 = Me (1h and 1i) reacted successfully with 2a to afford the corresponding dienes 3ha and 3ia in 84% and 89% yield, respectively. Sterically hindered tetrasubstituted α-allenyl acetates (1j to 1n, R1, R2 = −(CH2)n–, n = 4 or 5) were also suitable substrates for this reaction and furnished the 1,3-dienes (3ja to 3na) in yields from 59% to 91%. Notably, the reaction conditions were compatible with a Boc-protected (Boc = tert-butyloxylcarbonyl) cyclic amine, and 1,3-diene 3oa was obtained in 40% yield.

Scheme 2. Scope of α-Allenyl Esters.

Scheme 2

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Butanoate instead of acetate substrate was used.

With 1.0 mmol of 1.

Next, the scope of Grignard reagents was investigated (Scheme 3). Methyl magnesium bromide (2b) was a reactive nucleophile for this reaction and afforded 3ab in 90% yield with an E/Z ratio of 8.2:1. n-Butyl magnesium chloride (2c) bearing β-hydrogen atoms afforded the desired product in 63% yield and good E/Z ratio (10:1). Sterically hindered (2-methyl-2-phenylpropyl)magnesium chloride (2d) was also an applicable substrate, and the coupling product 3fd from 1f was isolated in 78% yield. (3-Phenylpropyl)magnesium chloride (2e) was successfully coupled with 1i, 1k, and 1l, giving the corresponding products 3ie, 3ke, and 3le in 64–92% yields in the presence of 1.0 mol % of Fe(acac)3. However, representative phenyl magnesium bromide (2f), ethyl magnesium bromide (2g), and α,α′-dioxo-ethyl magnesium bromide (2h) failed to give the desired products in practically useful yields with 1a.16

Scheme 3. Scope of Grignard Reagent.

Scheme 3

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With 1.0 mmol of 1.

With 1.0 mol % of Fe(acac)3.

Based on these results and our previous work on iron catalysis, a plausible mechanism of this iron-catalyzed 1,3-diene synthesis reaction is proposed (Scheme 4). The addition of Grignard reagent 2 to the solution of the precatalyst Fe(acac)3 forms a reduced organoiron intermediate (Bn-[Fe]nMgX), whose exact structure is still unclear. This catalytically active species attacks α-allenyl acetate 1 through a syn or anti SN2′ pathway to form intermediate int A (oxidative addition). The latter intermediate would predominantly be of E configuration, since the R group in the α-position would prefer to be anti to the allene moiety. Subsequent reductive elimination would deliver 3 and regenerate the catalyst. The preferred anti conformation of the allene part and the a-substituent R results in the E configuration of Cα=C1 independent of whether syn or anti SN2′ displacement occurs (Scheme 4). In the reaction with an α-allenyl acetate that has a substituent (R) in the 3-position, the SN2′ attack by Bn-[Fe]nMgX will occur from the face that avoids steric compulsion between the C3–R group and Bn-[Fe]nMX. The energetically favored pathway would lead to E configuration of C2=C3 (Scheme 5).

Scheme 4. Proposed Reaction Mechanism.

Scheme 4

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Scheme 5. Conformational Analysis for E/Z Stereoselectivity of C2=C3.

Scheme 5

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In summary, a simple and efficient approach to 1,3-dienes was realized through iron-catalyzed C–C bond coupling between α-allenyl acetates and Grignard reagents. A wide range of mono-, di-, tri-, and tetrasubstituted α-allenic acetates were applied, which led to the formation of structurally diverse 1,3-dienes. The reaction was associated with mild reaction conditions, high reactivity, good functional group compatibility, and easy scale up.

Acknowledgments

We are grateful for financial support from the Swedish Research Council (2019-04042), the Foundation Olle Engkvist Byggmästare, the Knut and Alice Wallenberg Foundation (KAW 2016.0072), and the Swedish Foundation for Strategic Environmental Research (Mistra: Project Mistra SafeChem, Project Number 2018/11).

Data Availability Statement

The data underlying this study are available in the published article and its online Supporting Information.

Supporting Information Available

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.orglett.2c03916.

  • Experimental procedures and spectral data for all new compounds (PDF)

Author Contributions

† WK and SNK contributed equally.

The authors declare no competing financial interest.

Supplementary Material

ol2c03916_si_001.pdf (4.5MB, pdf)

References

  1. a Zotchev B. S. Polyene Macrolide Antibiotics and their Applications in Human Therapy. Curr. Med. Chem. 2003, 10, 211–223. 10.2174/0929867033368448. [DOI] [PubMed] [Google Scholar]; b Thiele S. K. H.; Wilson D. R. Alternate Transition Metal Complex Based Diene Polymerization. Journal of Macromolecular Science, Part C 2003, 43, 581–628. 10.1081/MC-120025979. [DOI] [Google Scholar]; c Thirsk C.; Whiting A. Polyene Natural Products. J. Chem. Soc., Perkin Trans. 2002, 1, 999–1023. 10.1039/b109741p. [DOI] [Google Scholar]; d Rychnovsky S. D. Oxo Polyene Macrolide Antibiotics. Chem. Rev. 1995, 95, 2021–2040. 10.1021/cr00038a011. [DOI] [Google Scholar]
  2. a Nicolaou K. C.; Snyder S. A.; Montagnon T.; Vassilikogiannakis G. The Diels–Alder Reaction in Total Synthesis. Angew. Chem., Int. Ed. 2002, 41, 1668–1698. . [DOI] [PubMed] [Google Scholar]; b Corey E. J. Catalytic Enantioselective Diels–Alder Reactions: Methods, Mechanistic Fundamentals, Pathways, and Applications. Angew. Chem., Int. Ed. 2002, 41, 1650–1667. . [DOI] [PubMed] [Google Scholar]
  3. a Li M.-M.; Cheng L.; Xiao L.-J.; Xie J.-H.; Zhou Q.-L. Palladium-Catalyzed Asymmetric Hydrosulfonylation of 1,3-Dienes with Sulfonyl Hydrazides. Angew. Chem., Int. Ed. 2021, 60, 2948–2951. 10.1002/anie.202012485. [DOI] [PubMed] [Google Scholar]; b Perry G. J. P.; Jia T.; Procter D. J. Copper-Catalyzed Functionalization of 1,3-Dienes: Hydrofunctionalization, Borofunctionalization, and Difunctionalization. ACS Catal. 2020, 10, 1485–1499. 10.1021/acscatal.9b04767. [DOI] [Google Scholar]; c Cheng L.; Li M.-M.; Xiao L.-J.; Xie J.-H.; Zhou Q.-L. Nickel(0)-Catalyzed Hydroalkylation of 1,3-Dienes with Simple Ketones. J. Am. Chem. Soc. 2018, 140, 11627–11630. 10.1021/jacs.8b09346. [DOI] [PubMed] [Google Scholar]; d Huang L.; Arndt M.; Gooßen K.; Heydt H.; Gooßen L. J. Late Transition Metal-Catalyzed Hydroamination and Hydroamidation. Chem. Rev. 2015, 115, 2596–2697. 10.1021/cr300389u. [DOI] [PubMed] [Google Scholar]
  4. a Xiong Y.; Sun Y.; Zhang G. Recent Advances on Catalytic Asymmetric Difunctionalization of 1,3-Dienes. Tetrahedron Lett. 2018, 59, 347–355. 10.1016/j.tetlet.2017.12.059. [DOI] [Google Scholar]; b McNeill E.; Ritter T. 1,4-Functionalization of 1,3-Dienes With Low-Valent Iron Catalysts. Acc. Chem. Res. 2015, 48, 2330–2343. 10.1021/acs.accounts.5b00050. [DOI] [PubMed] [Google Scholar]
  5. a De Paolis M.; Chataigner I.; Maddaluno J.. Recent Advances in Stereoselective Synthesis of 1,3-Dienes. In Stereoselective Alkene Synthesis; Wang J., Ed.; Springer: Berlin Heidelberg, 2012; pp 87–146. [DOI] [PubMed] [Google Scholar]; b Maryanoff B. E.; Reitz A. B. The Wittig Olefination Reaction and Modifications Involving Phosphoryl-Stabilized Carbanions. Stereochemistry, Mechanism, and Selected Synthetic Aspects. Chem. Rev. 1989, 89, 863–927. 10.1021/cr00094a007. [DOI] [Google Scholar]
  6. a Hou C.-J.; Schuppe A. W.; Knippel J. L.; Ni A. Z.; Buchwald S. L. A Dual CuH- and Pd-Catalyzed Stereoselective Synthesis of Highly Substituted 1,3-Dienes. Org. Lett. 2021, 23, 8816–8821. 10.1021/acs.orglett.1c03324. [DOI] [PMC free article] [PubMed] [Google Scholar]; b Soengas R. G.; Rodríguez-Solla H. Modern Synthetic Methods for the Stereoselective Construction of 1,3-Dienes. Molecules 2021, 26, 249. 10.3390/molecules26020249. [DOI] [PMC free article] [PubMed] [Google Scholar]; c Nguyen V. T.; Dang H. T.; Pham H. H.; Nguyen V. D.; Flores-Hansen C.; Arman H. D.; Larionov O. V. Highly Regio- and Stereoselective Catalytic Synthesis of Conjugated Dienes and Polyenes. J. Am. Chem. Soc. 2018, 140, 8434–8438. 10.1021/jacs.8b05421. [DOI] [PMC free article] [PubMed] [Google Scholar]; d Liu M.; Yang P.; Karunananda M. K.; Wang Y.; Liu P.; Engle K. M. C(alkenyl)–H Activation via Six-Membered Palladacycles: Catalytic 1,3-Diene Synthesis. J. Am. Chem. Soc. 2018, 140, 5805–5813. 10.1021/jacs.8b02124. [DOI] [PMC free article] [PubMed] [Google Scholar]; e Olivares A. M.; Weix D. J. Multimetallic Ni- and Pd-Catalyzed Cross-Electrophile Coupling To Form Highly Substituted 1,3-Dienes. J. Am. Chem. Soc. 2018, 140, 2446–2449. 10.1021/jacs.7b13601. [DOI] [PMC free article] [PubMed] [Google Scholar]; f Hu X.-H.; Zhang J.; Yang X.-F.; Xu Y.-H.; Loh T.-P. Stereo- and Chemoselective Cross-Coupling between Two Electron-Deficient Acrylates: An Efficient Route to (Z,E)-Muconate Derivatives. J. Am. Chem. Soc. 2015, 137, 3169–3172. 10.1021/ja512237d. [DOI] [PubMed] [Google Scholar]; g Delcamp J. H.; Gormisky P. E.; White M. C. Oxidative Heck Vinylation for the Synthesis of Complex Dienes and Polyenes. J. Am. Chem. Soc. 2013, 135, 8460–8463. 10.1021/ja402891m. [DOI] [PMC free article] [PubMed] [Google Scholar]; h Zheng C.; Wang D.; Stahl S. S. Catalyst-Controlled Regioselectivity in the Synthesis of Branched Conjugated Dienes via Aerobic Oxidative Heck Reactions. J. Am. Chem. Soc. 2012, 134, 16496–16499. 10.1021/ja307371w. [DOI] [PMC free article] [PubMed] [Google Scholar]; i Stang E. M.; White M. C. Molecular Complexity via C–H Activation: A Dehydrogenative Diels–Alder Reaction. J. Am. Chem. Soc. 2011, 133, 14892–14895. 10.1021/ja2059704. [DOI] [PMC free article] [PubMed] [Google Scholar]; j Hansen A. L.; Ebran J.-P.; Ahlquist M.; Norrby P.-O.; Skrydstrup T. Heck Coupling with Nonactivated Alkenyl Tosylates and Phosphates: Examples of Effective 1,2-Migrations of the Alkenyl Palladium(II) Intermediates. Angew. Chem., Int. Ed. 2006, 45, 3349–3353. 10.1002/anie.200600442. [DOI] [PubMed] [Google Scholar]; k Molander G. A.; Felix L. A. Stereoselective Suzuki–Miyaura Cross-Coupling Reactions of Potassium Alkenyltrifluoroborates with Alkenyl Bromides. J. Org. Chem. 2005, 70, 3950–3956. 10.1021/jo050286w. [DOI] [PubMed] [Google Scholar]
  7. a Huang Q.; Su Y.-X.; Sun W.; Hu M.-Y.; Wang W.-N.; Zhu S.-F. Iron-Catalyzed Vinylzincation of Terminal Alkynes. J. Am. Chem. Soc. 2022, 144, 515–526. 10.1021/jacs.1c11072. [DOI] [PubMed] [Google Scholar]; b Guo Z.; Wen H.; Liu G.; Huang Z. Iron-Catalyzed Regio- and Stereoselective Hydrosilylation of 1,3-Enynes To Access 1,3-Dienylsilanes. Org. Lett. 2021, 23, 2375–2379. 10.1021/acs.orglett.1c00670. [DOI] [PubMed] [Google Scholar]
  8. a Xu G.-L.; Duan Y.-T.; Wang Z.-X. Copper-Catalyzed Reaction of 2,3-Allenols with Silylzinc Reagents: Access to 2-Silyl-1,3-butadienes. Org. Lett. 2022, 24, 7934–7938. 10.1021/acs.orglett.2c03041. [DOI] [PubMed] [Google Scholar]; b Jia J.; Yuan F.; Zhang Z.; Song X.; Hu F.; Xia Y. Copper-Catalyzed Ring-Opening Defluoroborylation of gem-Difluorinated Cyclobutenes: A General Route to Bifunctional 1,3-Dienes and Their Applications. Org. Lett. 2022, 24, 1985–1990. 10.1021/acs.orglett.2c00403. [DOI] [PubMed] [Google Scholar]; c Shan Q.-C.; Hu L.-M.; Qin W.; Hu X.-H. Copper-Catalyzed Cross-Nucleophile Coupling of β-Allenyl Silanes with Tertiary C–H Bonds: A Radical Approach to Branched 1,3-Dienes. Org. Lett. 2021, 23, 6041–6045. 10.1021/acs.orglett.1c02112. [DOI] [PubMed] [Google Scholar]; d Guo K.; Kleij A. W. Copper-Mediated Dichotomic Borylation of Alkyne Carbonates: Stereoselective Access to (E)-1,2-Diborylated 1,3-Dienes versus Traceless Monoborylation Affording α-Hydroxyallenes. Angew. Chem., Int. Ed. 2021, 60, 4901–4906. 10.1002/anie.202014310. [DOI] [PubMed] [Google Scholar]; e Chaves-Pouso A.; Rivera-Chao E.; Fañanás-Mastral M. Copper-catalyzed protoboration of borylated dendralenes: a regio- and stereoselective access to functionalized 1,3-dienes. Chem. Commun. 2020, 56, 12230–12233. 10.1039/D0CC04018E. [DOI] [PubMed] [Google Scholar]; f Chen F.; Xia Y.; Lin R.; Gao Y.; Xu P.; Zhao Y. Copper-Catalyzed Direct Twofold C–P Cross-Coupling of Unprotected Propargylic 1,4-Diols: Access to 2,3-Bis(diarylphosphynyl)-1,3-butadienes. Org. Lett. 2019, 21, 579–583. 10.1021/acs.orglett.8b03985. [DOI] [PubMed] [Google Scholar]; g Semba K.; Fujihara T.; Terao J.; Tsuji Y. Copper-Catalyzed Borylation of α-Alkoxy Allenes with Bis(pinacolato)diboron: Efficient Synthesis of 2-Boryl 1,3-Butadienes. Angew. Chem., Int. Ed. 2013, 52, 12400–12403. 10.1002/anie.201306843. [DOI] [PubMed] [Google Scholar]
  9. a Zhou Z.; Chen J.; Chen H.; Kong W. Stereoselective Synthesis of Pentasubstituted 1,3-Dienes via Ni-catalyzed Reductive Coupling of Unsymmetrical Internal Alkynes. Chem. Sci. 2020, 11, 10204–10211. 10.1039/D0SC04173D. [DOI] [PMC free article] [PubMed] [Google Scholar]; b Chen Y.; Dang L.; Ho C.-Y. NHC-Ni Catalyzed Enantioselective Synthesis of 1,4-Dienes by Cross-Hydroalkenylation of Cyclic 1,3-Dienes and Heterosubstituted Terminal Olefins. Nat. Commun. 2020, 11, 2269. 10.1038/s41467-020-16139-2. [DOI] [PMC free article] [PubMed] [Google Scholar]; c Francos J.; Cadierno V. Nickel-Catalyzed Homocoupling of (Z)-β-Iodoenol Esters: Stereoselective Access to (Z, Z)-Buta-1, 3-diene-1, 4-diyl diesters. Synthesis 2019, 51, 3117–3126. 10.1055/s-0037-1610709. [DOI] [Google Scholar]; d Watabe Y.; Kanazawa K.; Fujita T.; Ichikawa J. Nickel-Catalyzed Hydroalkenylation of Alkynes through C–F Bond Activation: Synthesis of 2-Fluoro-1, 3-dienes. Synthesis 2017, 49, 3569–3575. 10.1055/s-0036-1588842. [DOI] [Google Scholar]; e Kawashima T.; Ohashi M.; Ogoshi S. Nickel-Catalyzed Formation of 1,3-Dienes via a Highly Selective Cross-Tetramerization of Tetrafluoroethylene, Styrenes, Alkynes, and Ethylene. J. Am. Chem. Soc. 2017, 139, 17795–17798. 10.1021/jacs.7b12007. [DOI] [PubMed] [Google Scholar]; f Ogata K.; Murayama H.; Sugasawa J.; Suzuki N.; Fukuzawa S.-i. Nickel-Catalyzed Highly Regio- and Stereoselective Cross-Trimerization between Triisopropylsilylacetylene and Internal Alkynes Leading to 1,3-Diene-5-ynes. J. Am. Chem. Soc. 2009, 131, 3176–3177. 10.1021/ja900146u. [DOI] [PubMed] [Google Scholar]; g Ananikov V. P.; Orlov N. V.; Kabeshov M. A.; Beletskaya I. P.; Starikova Z. A. Stereodefined Synthesis of a New Type of 1,3-Dienes by Ligand-Controlled Carbon–Carbon and Carbon–Heteroatom Bond Formation in Nickel-Catalyzed Reaction of Diaryldichalcogenides with Alkynes. Organometallics 2008, 27, 4056–4061. 10.1021/om800282h. [DOI] [Google Scholar]; h Ikeda Y.; Ukai J.; Ikeda N.; Yamamoto H. Stereoselective Synthesis of 1,4-Disubstituted 1,3-Diene from Aldehyde Using Organotitanium Reagent. Tetrahedron 1987, 43, 731–741. 10.1016/S0040-4020(01)90007-9. [DOI] [Google Scholar]
  10. a Fürstner A. Iron Catalyzed C–C-Bond Formation: From Canonical Cross Coupling to a Quest for New Reactivity. Bull. Chem. Soc. Jpn. 2021, 94, 666–677. 10.1246/bcsj.20200319. [DOI] [Google Scholar]; b Sandl S.; Jacobi von Wangelin A. The Role of Organoferrates in Iron-Catalyzed Cross-Couplings. Angew. Chem., Int. Ed. 2020, 59, 5434–5437. 10.1002/anie.201914844. [DOI] [PubMed] [Google Scholar]; c Neidig M. L.; Carpenter S. H.; Curran D. J.; DeMuth J. C.; Fleischauer V. E.; Iannuzzi T. E.; Neate P. G.; Sears J. D.; Wolford N. J. Development and Evolution of Mechanistic Understanding in Iron-Catalyzed Cross-Coupling. Acc. Chem. Res. 2019, 52, 140–150. 10.1021/acs.accounts.8b00519. [DOI] [PMC free article] [PubMed] [Google Scholar]
  11. a Manna S.; Kong W.-J.; Bäckvall J.-E. Iron (II)-Catalyzed Aerobic Biomimetic Oxidation of N-Heterocycles. Chem. Eur. J. 2021, 27, 13725–13729. 10.1002/chem.202102483. [DOI] [PMC free article] [PubMed] [Google Scholar]; b Gudmundsson A.; Manna S.; Bäckvall J. E. Iron (II)-Catalyzed Aerobic Biomimetic Oxidation of Amines using a Hybrid Hydroquinone/Cobalt Catalyst as Electron Transfer Mediator. Angew. Chem. 2021, 133, 11925–11929. 10.1002/ange.202102681. [DOI] [PMC free article] [PubMed] [Google Scholar]; c Gudmundsson A.; Schlipköter K. E.; Bäckvall J.-E. Iron(II)-Catalyzed Biomimetic Aerobic Oxidation of Alcohols. Angew. Chem., Int. Ed. 2020, 59, 5403–5406. 10.1002/anie.202000054. [DOI] [PMC free article] [PubMed] [Google Scholar]; d Jiang X.; Zhang J.; Ma S. Iron Catalysis for Room-Temperature Aerobic Oxidation of Alcohols to Carboxylic Acids. J. Am. Chem. Soc. 2016, 138, 8344–8347. 10.1021/jacs.6b03948. [DOI] [PubMed] [Google Scholar]
  12. a Shang R.; Ilies L.; Nakamura E. Iron-Catalyzed C–H Bond Activation. Chem. Rev. 2017, 117, 9086–9139. 10.1021/acs.chemrev.6b00772. [DOI] [PubMed] [Google Scholar]; b Cera G.; Ackermann L.. Iron-Catalyzed C–H Functionalization Processes. In Ni- and Fe-Based Cross-Coupling Reactions; Springer, 2017; pp 191–224. [Google Scholar]
  13. a Isomura M.; Petrone D. A.; Carreira E. M. Construction of Vicinal Quaternary Centers via Iridium-Catalyzed Asymmetric Allenylic Alkylation of Racemic Tertiary Alcohols. J. Am. Chem. Soc. 2021, 143, 3323–3329. 10.1021/jacs.1c00609. [DOI] [PubMed] [Google Scholar]; b Petrone D. A.; Isomura M.; Franzoni I.; Rössler S. L.; Carreira E. M. Allenylic Carbonates in Enantioselective Iridium-Catalyzed Alkylations. J. Am. Chem. Soc. 2018, 140, 4697–4704. 10.1021/jacs.8b01416. [DOI] [PubMed] [Google Scholar]; c Li Q.; Fu C.; Ma S. Catalytic Asymmetric Allenylation of Malonates with the Generation of Central Chirality. Angew. Chem., Int. Ed. 2012, 51, 11783–11786. 10.1002/anie.201204346. [DOI] [PubMed] [Google Scholar]; d Nemoto T.; Kanematsu M.; Tamura S.; Hamada Y. Palladium-Catalyzed Asymmetric Allylic Alkylation of 2, 3-Allenyl Acetates Using a Chiral Diaminophosphine Oxide. Adv. Synth. Catal. 2009, 351, 1773–1778. 10.1002/adsc.200900151. [DOI] [Google Scholar]; e Trost B. M.; Fandrick D. R.; Dinh D. C. Dynamic Kinetic Asymmetric Allylic Alkylations of Allenes. J. Am. Chem. Soc. 2005, 127, 14186–14187. 10.1021/ja0543705. [DOI] [PubMed] [Google Scholar]; f Kezuka S.; Kanemoto K.; Takeuchi R. Iridium Complex-Catalyzed Method for the Construction of a Quaternary Carbon Center α to Allene. Tetrahedron Lett. 2004, 45, 6403–6406. 10.1016/j.tetlet.2004.07.002. [DOI] [Google Scholar]; g Imada Y.; Ueno K.; Kutsuwa K.; Murahashi S.-I. Palladium-Catalyzed Asymmetric Alkylation of 2,3-Alkadienyl Phosphates. Synthesis of Optically Active 2-(2,3-Alkadienyl)malonates. Chem. Lett. 2002, 31, 140–141. 10.1246/cl.2002.140. [DOI] [Google Scholar]
  14. a Alonso J. M.; Almendros P. Deciphering the Chameleonic Chemistry of Allenols: Breaking the Taboo of a Onetime Esoteric Functionality. Chem. Rev. 2021, 121, 4193–4252. 10.1021/acs.chemrev.0c00986. [DOI] [PMC free article] [PubMed] [Google Scholar]; b Shukla R. K.; Nair A. M.; Khan S.; Volla C. M. Cobalt-Catalyzed C8-Dienylation of Quinoline-N-Oxides. Angew. Chem., Int. Ed. 2020, 132, 17190–17196. 10.1002/ange.202003216. [DOI] [PubMed] [Google Scholar]; c Lippincott D. J.; Linstadt R. T.; Maser M. R.; Gallou F.; Lipshutz B. H. Synthesis of Functionalized 1, 3-Butadienes via Pd-Catalyzed Cross-Couplings of Substituted Allenic Esters in Water at Room Temperature. Org. Lett. 2018, 20, 4719–4722. 10.1021/acs.orglett.8b01377. [DOI] [PubMed] [Google Scholar]; d Sim S. H.; Park H.-J.; Lee S. I.; Chung Y. K. Palladium (0)-Catalyzed Decarboxylation of Buta-2, 3-dienyl 2’-Alkynoates: Approach to the Synthesis of 2-Alkynyl Buta-1, 3-dienes. Org. Lett. 2008, 10, 433–436. 10.1021/ol702577g. [DOI] [PubMed] [Google Scholar]; e Schneekloth J. S. Jr; Pucheault M.; Crews C. M. Construction of Highly Substituted Stereodefined Dienes by Cross-Coupling of α-Allenic Acetates. Eur. J. Org. Chem. 2007, 2007, 40–43. 10.1002/ejoc.200600721. [DOI] [Google Scholar]; f Moriya T.; Furuuchi T.; Miyaura N.; Suzuki A. A New Facile Synthesis of 2-Substituted 1, 3-Butadiene Derivatives via Palladium-Catalyzed Cross-Coupling Reaction of 2, 3-Alkadienyl Carbonates with Organoboron Compounds. Tetrahedron 1994, 50, 7961–7968. 10.1016/S0040-4020(01)85281-9. [DOI] [Google Scholar]; g Djahanbini D.; Cazes B.; Gore J. Reactive D’esters α-Alleniques. Synthese regiospecifique de diesters γ-alleniques et de dienes–1,3. Tetrahedron Lett. 1984, 25, 203–206. 10.1016/S0040-4039(00)99840-X. [DOI] [Google Scholar]
  15. a Kessler S. N.; Hundemer F.; Bäckvall J.-E. A Synthesis of Substituted α-Allenols via Iron-Catalyzed Cross-Coupling of Propargyl Carboxylates with Grignard Reagents. ACS Catal. 2016, 6, 7448–7451. 10.1021/acscatal.6b02114. [DOI] [PMC free article] [PubMed] [Google Scholar]; b Kessler S. N.; Bäckvall J.-E. Iron-catalyzed Cross-Coupling of Propargyl Carboxylates and Grignard Reagents: Synthesis of Substituted Allenes. Angew. Chem., Int. Ed. 2016, 55, 3734–3738. 10.1002/anie.201511139. [DOI] [PMC free article] [PubMed] [Google Scholar]; c Posevins D.; Bermejo-López A.; Bäckvall J.-E. Iron-Catalyzed Cross-Coupling of Propargyl Ethers with Grignard Reagents for the Synthesis of Functionalized Allenes and Allenols. Angew. Chem., Int. Ed. 2021, 60, 22178–22183. 10.1002/anie.202106742. [DOI] [PMC free article] [PubMed] [Google Scholar]
  16. With phenyl or ethyl Grignard reagent, a complex mixture was obtained and the starting material 1a was completely decomposed. With dioxethyl Grignard reagent 2h, more than 94% of 1a was recovered.

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