Skip to main content
NCBI home page
ACS AuthorChoice logoLink to ACS AuthorChoice
. 2022 Jun 17;24(25):4513–4518. doi: 10.1021/acs.orglett.2c01477

Silver-Catalyzed Controlled Intermolecular Cross-Coupling of Silyl Enol Ethers: Scalable Access to 1,4-Diketones

Li Xu †, Xiaoyi Liu †, Gregory R Alvey ‡, Andrey Shatskiy ‡, Jian-Quan Liu †,‡,*, Markus D Kärkäs ‡,*, Xiang-Shan Wang †,*
PMCID: PMC9536665  PMID: 35713416

Abstract

graphic file with name ol2c01477_0006.jpg

A protocol for silver-catalyzed controlled intermolecular cross-coupling of silyl enolates is disclosed. The protocol displays good functional group tolerance and allows efficient preparation of a series of synthetically useful 1,4-diketones. Preliminary mechanistic investigations suggest that the reaction proceeds through a one-electron process involving free radical species in which PhBr acts as the oxidant.

Metal-catalyzed cross-couplings and related reactions involving carbon-based nucleophilic reagents are widely employed in academia and industry.1 Cross-coupling reactions remain one of the most vibrant areas of chemistry and enable straightforward preparation of, for example, pharmaceuticals, agrochemicals, and materials. However, cross-coupling reactions that utilize coupling partners of a similar chemical nature are frequently accompanied by undesired homocoupling reactions. Therefore, further advancements in cross-coupling technologies to involve alternative precursors and more versatile reaction systems are required.

Enolates make up a multifaceted class of building blocks in organic synthesis and are widely applied in cross-coupling manifolds. Significant progress in cross-coupling reactions of enolates with electrophiles or free radical species has been detailed.2,3 These reactions allow various synthetic manipulations, enabling access to α-functionalized carbonyl compounds, which function as critical synthetic intermediates in the preparation of various natural products and pharmacophores.4 Oxidative cross-coupling of carbon-centered nucleophiles constitutes an excellent approach for forging new carbon–carbon bonds, providing a strategic alternative to conventional nucleophile–electrophile coupling reactions. However, selective intermolecular cross-coupling of two different enolate equivalents encompasses a significant challenge due to the similarities in the steric and electronic properties of the two coupling partners.5 To the best of our knowledge, only a handful of reports detailing the cross-coupling of two different enolates or enolate equivalents have been disclosed.6 For example, in 1975, Saegusa and co-workers reported the pioneering work on intermolecular cross-coupling of two distinct enolates to furnish unsymmetrical 1,4-diketone scaffolds.7 In this strategy, suppressing the homocoupling reactions was achieved by utilizing a large excess of one of the coupling partners, thus significantly reducing the atom economy of the developed process. Later, Ruzziconi8 and Ohshiro9 also achieved oxidative cross-coupling of two different trimethylsilyl enol ethers that is promoted by ceric and oxovanadium oxidants, respectively. Thereafter, Schmittel and co-workers established an unprecedented method for oxidative intramolecular cyclization of silyl bis-enol ethers.10 Thomson and Wirth independently made use of an intramolecular traceless silicon tether to connect two different enolates, rendering the reaction intramolecular and neatly avoiding selectivity-related issues (Figure 1).11,12 However, these protocols require elaborate substrate feedstocks that rely on multistep preparation. Furthermore, Hirao and Amaya reported the vanadium-induced intermolecular cross-coupling of two different enolates, capitalizing on the differences in reactivity between silyl- and boron-based enolate equivalents (Figure 1).13 Recently, Szpilman and co-workers disclosed a procedure for oxidative cross-coupling of two different enolate equivalents using a hypervalent iodine(III) compound (Koser’s reagent).14 However, this reaction requires extremely low temperatures and sequential addition of the coupling partners, decreasing the practicality of the disclosed protocol (Figure 1). Herein, we alleviate the drawbacks of the previously described cross-coupling manifolds of silyl enol ethers with the use of silver catalysis,15,16 providing a convenient method for the chemoselective preparation of a broad range of 1,4-dicarbonyl scaffolds under mild reaction conditions and using near-stoichiometric amounts of the two coupling partners (Figure 1).

Figure 1.

Figure 1

Open in a new tab

Oxidative cross-coupling strategies for the synthesis of 1,4-diketones.

At the beginning of our investigations, silyl enol ethers 1a and 2a were selected as model substrates to optimize the oxidative cross-coupling reaction (Table 1). To our delight, conducting the reaction in DMSO at 100 °C under air in the presence of AgF (30 mol %) and bromobenzene (2 equiv) exclusively afforded the desired 1,4-diketone 3a in 9% isolated yield after 6 h, accompanied by the generation of homocoupling product 3s in <5% yield (Table 1, entry 1). Performing the reaction under argon afforded the desired 1,4-diketone 3a in 21% yield and homocoupling product 3s in 11% yield (Table 1, entry 2). Encouraged by this result, we surveyed other silver-based precursors, including Ag2CO3, AgOTf, AgBF4, and AgOAc, and found that AgF displays the best reactivity while the others proved to be less efficient (Table 1, entries 3–6, respectively). Other metal-based catalysts, including InCl3, Cu(OTf)2, CuI, and Pd(OAc)2, provided a complex mixture of products and only trace amounts of product 3a (Table 1, entries 7–10, respectively). Subsequently, switching the solvent to MeCN greatly increased the yield of cross-coupling product 3a to 42% (Table 1, entry 11). In contrast, the use of aprotic or polar solvents, such as DMF, toluene, and DCE, had a negative effect on the reaction (Table 1, entries 12–14, respectively), while employing the protic solvent EtOH completely inhibited the reaction (Table 1, entry 15). Decreasing the reaction temperature from 100 °C to room temperature significantly improved the yield of the desired product 3a to 72% (Table 1, entries 16–19), while decreasing the catalyst loading from 30 to 20 mol % had an insignificant influence on the reaction outcome (Table 1, entry 20). A control experiment in the absence of bromobenzene provided only trace amounts of the cross-coupling product (Table 1, entry 22), thus indicating that bromobenzene plays a critical role in the reaction.17,18

Table 1. Optimization of the Reaction Conditionsa.

graphic file with name ol2c01477_0004.jpg

        yield (%)b
entry [M] solvent temp (°C) 3a 3s
1c AgF DMSO 100 9 <5
2 AgF DMSO 100 21 11
3 Ag2CO3 DMSO 100 13 8
4 AgOTf DMSO 100 0 0
5 AgBF4 DMSO 100 0 0
6 AgOAc DMSO 100 15 9
7 InCl3 DMSO 100 0 0
8 Cu(OTf)2 DMSO 100 0 0
9 CuI DMSO 100 0 0
10 Pd(OAc)2 DMSO 100 0 0
11 AgF MeCN 100 42 29
12 AgF DMF 100 28 21
13 AgF toluene 100 35 26
14 AgF DCE 100 27 13
15 AgF EtOH 100 0 0
16 AgF MeCN 80 47 31
17 AgF MeCN 60 53 27
18 AgF MeCN 40 64 25
19 AgF MeCN rt 72 19
20d AgF MeCN rt 69 23
21e AgF MeCN rt 43 28
22f AgF MeCN rt 0 0
23 AgBr MeCN rt 23 12
Open in a new tab
a

Reactions were carried out with 1a (0.65 mmol), 2a (0.5 mmol), catalyst (30 mol %), and PhBr (1.0 mmol) in solvent (2.0 mL) under argon for 6 h.

b

Isolated yields of 3a after purification by column chromatography.

c

Reactions carried out under air.

d

With 20 mol % catalyst.

e

With 10 mol % catalyst.

f

Reaction carried out in the absence of PhBr.

With the optimized reaction conditions in hand, we explored the generality of the established protocol (Scheme 1). An array of diversely functionalized silyl enol ethers 1 engaged in the desired cross-coupling reaction with silyl enol ethers 2 to afford the corresponding products 3 in good to excellent yields (Scheme 1). For example, aryl-based silyl enol ether motifs bearing electron-donating or electron-withdrawing moieties were tolerated in the cross-coupling reaction with 1a to produce the corresponding products 3b–3h in good yields. Gratifyingly, the utilization of heteroaryl silyl ethers, including 2-furyl and 2-thienyl, afforded the corresponding adducts 3i and 3j, respectively, illustrating the compatibility of the developed protocol. Subjecting alkyl-based silyl enol ethers to aryl-based silyl enol ethers generated the desired products 3q and 3r in good to excellent yields. Furthermore, the homocoupling reaction with aryl-based silyl enol ethers proceeds efficiently and yields the target compounds in ≤93% yield (Scheme 1). Finally, the structure of products 3 was supported through X-ray analysis of product 3ab [CCDC 2143818 (see Scheme 1)]. To further explore the synthetic utility of the developed protocol, the applicability of the silver-catalyzed method was highlighted through a gram-scale reaction of 1a and 2a (Scheme 1). The reaction was performed on a 5 mmol scale and proceeded smoothly to give product 3a (0.86 g, 64%). The highly functionalized 1,4-diketones developed by this protocol provide opportunities for a range of further synthetic manipulations, especially for heterocycle synthesis. For instance, synthetic conversion of diketone 3a into functionalized pyrrole 4 and furan 5 was achieved in high yields by subjecting the diketone to ammonium acetate and triflic acid, respectively.19

Scheme 1. Silver-Catalyzed Synthesis of 1,4-Diketones.

Scheme 1

Open in a new tab

All reactions were carried out with 1a (0.65 mmol), 2a (0.5 mmol), and AgF (20 mol %) in CH3CN (2.0 mL) at room temperature under air for 6 h. Yields are of isolated products after purification by column chromatography.

Yields are of isolated homocoupling products of 1.

Reactions carried out at room temperature for 24 h.

Additional experiments were performed to gain insight into the mechanism of the developed transformation (Scheme 2). The silver-catalyzed homocoupling reaction of silyl enol ethers 1a was completely suppressed by the addition of radical inhibitor TEMPO, indicating that the reaction proceeds through a free radical pathway.20 Additionally, we isolated TEMPO-based adduct 6 in 50% yield. To gain additional support for the proposed mechanism, ESI-MS experiments were performed, allowing detection of the phenyltrimethylsilane (PhTMS) byproduct (see Scheme 2 and Figure S1).21 Furthermore, when the reaction was conducted under the optimized conditions using AgBr as the silver precursor (Table 1, entry 23), only a small amount of the coupling product was produced, highlighting the essential role of fluoride for effective catalytic turnover. Also, we surmise that the developed reaction likely requires a nucleophilic counterion to mediate the desilylation of one of the silyl enol ethers upon conversion of Ag(II) intermediate A into AgF. Accordingly, while carbonate and acetate have sufficient nucleophilic character, OTf and BF4 cannot facilitate such a process (cf. Table 1, entries 3–6). Finally, considering the possible involvement of Ag(0) in the reaction, such processes would likely (although not necessarily) produce a silver mirror, as has been observed in our previous reports featuring catalytic amounts of Ag(I) catalysts.22 However, the formation of a silver mirror was not observed for the developed silyl enol ether cross-coupling reaction.

Scheme 2. Radical Trapping Experiments and Proposed Mechanism.

Scheme 2

Open in a new tab

On the basis of the experimental results and literature precedents,18,23 a plausible mechanism for the cross-coupling reaction between 1 and 2 was proposed (Scheme 2). Initially, AgF abstracts a bromine atom from PhBr to generate Ag(II) intermediate A and a phenyl radical. Then, the transiently formed phenyl radical reacts with silyl enol ether 1 to furnish α-carbonyl radical B along with PhTMS. Finally, α-carbonyl radical B undergoes radical addition to silyl enol ether 2 to form carbon-centered radical C, which undergoes one-electron oxidation by Ag(II) species A to form cross-coupling product 3 along with regeneration of Ag(I), thereby closing the catalytic cycle. Preliminary mechanistic studies support the events mentioned above; however, further studies are required to elucidate the mechanism of this intriguing reaction. It is also possible that a radical–radical coupling mechanism could be operating under the disclosed reaction conditions, competing with the proposed mechanism. However, given the observed high selectivity, such a mechanism is not likely to play the key role.

In conclusion, we have developed a silver-catalyzed procedure for controlled intermolecular cross-coupling of silyl enol ethers. The protocol exhibits good functional group tolerance, allowing access to a range of synthetically valuable 1,4-diketones. A plausible free radical-based pathway is proposed in which PhBr acts as the oxidant. The disclosed method presents a versatile framework for oxidative carbon–carbon bond formation from unpretentious starting materials. It is anticipated that this reaction manifold will stimulate several new synthetic strategies. Further investigations of the reaction are ongoing in our laboratories.

Acknowledgments

This work was financially supported by the Outstanding Youth Fund of Jiangsu Province (BK20211607), the NSFC (21702078), the 2021 National and Provincial College Students Innovation and Entrepreneurship Training Program (202110320010Z), the Priority Academic Program Development of Jiangsu Higher Education Institutions, FORMAS (Grant 2019-01269), the Swedish Research Council (Grant 2020-04764), the Olle Engkvist Foundation, the Magnus Bergvall Foundation, and KTH Royal Institute of Technology. The Wenner-Gren Foundations are kindly acknowledged for a postdoctoral fellowship to J.-Q.L.

Supporting Information Available

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.orglett.2c01477.

  • Experimental procedures and characterization data for all of the compounds (PDF)

The authors declare no competing financial interest.

Supplementary Material

ol2c01477_si_001.pdf (3.1MB, pdf)

References

  1. Liu C.; Zhang H.; Shi W.; Lei A. Bond Formations between Two Nucleophiles: Transition Metal Catalyzed Oxidative Cross-Coupling Reactions. Chem. Rev. 2011, 111, 1780–1824. 10.1021/cr100379j. [DOI] [PubMed] [Google Scholar]
  2. For selected examples of electrophiles, see:; a Wang P.-Y.; Massad I.; Marek I. Stereoselective Sc(OTf)3-Catalyzed Aldol Reactions of Disubstituted Silyl Enol Ethers of Aldehydes with Acetals. Angew. Chem., Int. Ed. 2021, 60, 12765–12769. 10.1002/anie.202101634. [DOI] [PubMed] [Google Scholar]; b Kou X.; Kou K. G. M. α-Arylation of Silyl Enol Ethers via Rhodium(III)-Catalyzed C–H Functionalization. ACS. Catal. 2020, 10, 3103–3109. 10.1021/acscatal.9b05622. [DOI] [Google Scholar]; c Nishimoto Y.; Kita Y.; Ueda H.; Imaoka H.; Chiba K.; Yasuda M.; Baba A. Coupling Reaction of Enol Derivatives with Silyl Ketene Acetals Catalyzed by Gallium Trihalides. Chem. - Eur. J. 2016, 22, 11837–11845. 10.1002/chem.201602150. [DOI] [PubMed] [Google Scholar]; d Guo F.; Clift M. D.; Thomson R. J. Oxidative Coupling of Enolates, Enol Silanes, and Enamines: Methods and Natural Product Synthesis. Eur. J. Org. Chem. 2012, 2012, 4881–4896. 10.1002/ejoc.201200665. [DOI] [PMC free article] [PubMed] [Google Scholar]; e Huang L.; Zhang X.; Zhang Y. CuBr-Catalyzed Reaction of N,N-Dimethylanilines and Silyl Enol Ethers: An Alternative Route to β-Arylamino Ketones. Org. Lett. 2009, 11, 3730–3733. 10.1021/ol901347t. [DOI] [PubMed] [Google Scholar]; f DeMartino M. P.; Chen K.; Baran P. S. Intermolecular Enolate Heterocoupling: Scope, Mechanism, and Application. J. Am. Chem. Soc. 2008, 130, 11546–11560. 10.1021/ja804159y. [DOI] [PubMed] [Google Scholar]
  3. For selected examples of free radical species, see:; a Fu M.-C.; Shang R.; Zhao B.; Wang B.; Fu Y. Photocatalytic Decarboxylative Alkylations mediated by Triphenylphosphine and Sodium Iodide. Science. 2019, 363, 1429–1434. 10.1126/science.aav3200. [DOI] [PubMed] [Google Scholar]; b Luo Q.; Mao R.; Zhu Y.; Wang Y. Photoredox-Catalyzed Generation of Sulfamyl Radicals: Sulfonamidation of Enol Silyl Ether with Chlorosulfonamide. J. Org. Chem. 2019, 84, 13897–13907. 10.1021/acs.joc.9b02062. [DOI] [PubMed] [Google Scholar]; c Yu W.; Ouyang Y.; Xu X.-H.; Qing F.-L. Visible Light-Induced Methoxycarbonyldifluoromethylation of Trimethylsilyl Enol Ethers and Allyltrimethylsilanes with FSO2CF2CO2Me. Chin. J. Chem. 2018, 36, 1024–1030. 10.1002/cjoc.201800318. [DOI] [Google Scholar]; d Scherbinina S. I.; Fedorov O. V.; Levin V. V.; Kokorekin V. A.; Struchkova M. I.; Dilman A. D. Synthesis of 3-Fluoropyridines via Photoredox-Mediated Coupling of α,α-Difluoro-β-iodoketones with Silyl Enol Ethers. J. Org. Chem. 2017, 82, 12967–12974. 10.1021/acs.joc.7b02467. [DOI] [PubMed] [Google Scholar]; e Esumi N.; Suzuki K.; Nishimoto Y.; Yasuda M. Synthesis of 1,4-Dicarbonyl Compounds from Silyl Enol Ethers and Bromocarbonyls, Catalyzed by an Organic Dye under Visible-Light Irradiation with Perfect Selectivity for the Halide Moiety over the Carbonyl Group. Org. Lett. 2016, 18, 5704–5707. 10.1021/acs.orglett.6b02869. [DOI] [PubMed] [Google Scholar]
  4. a Guo F.; Clift M. D.; Thomson R. J. Oxidative Coupling of Enolates, Enol Silanes, and Enamines: Methods and Natural Product Synthesis. Eur. J. Org. Chem. 2012, 2012, 4881–4896. 10.1002/ejoc.201200665. [DOI] [PMC free article] [PubMed] [Google Scholar]; b DeMartino M. P.; Chen K.; Baran P. S. Intermolecular Enolate Heterocoupling: Scope, Mechanism, and Application. J. Am. Chem. Soc. 2008, 130, 11546–11560. 10.1021/ja804159y. [DOI] [PubMed] [Google Scholar]
  5. Baran P. S.; DeMartino M. P. Intermolecular Oxidative Enolate Heterocoupling. Angew. Chem., Int. Ed. 2006, 45, 7083–7086. 10.1002/anie.200603024. [DOI] [PubMed] [Google Scholar]
  6. a Saito M.; Kobayashi Y.; Tsuzuki S.; Takemoto Y. Electrophilic Activation of Iodonium Ylides by Halogen-Bond-Donor Catalysis for Cross-Enolate Coupling. Angew. Chem., Int. Ed. 2017, 56, 7653–7657. 10.1002/anie.201703641. [DOI] [PubMed] [Google Scholar]; b Mao S.; Gao Y.-R.; Zhang S.-L.; Guo D.-D.; Wang Y.-Q. Copper(II)-Promoted C–C Bond Formation by Oxidative Coupling of Two C(sp3)–H Bonds Adjacent to Carbonyl Group to Construct 1,4-Diketones and Tetrasubstituted Furans. Eur. J. Org. Chem. 2015, 2015, 876–885. 10.1002/ejoc.201403274. [DOI] [Google Scholar]; c Casey B. M.; Flowers R. A. On the Nature of the Oxidative Heterocoupling of Lithium Enolates. J. Am. Chem. Soc. 2011, 133, 11492–11495. 10.1021/ja205017e. [DOI] [PMC free article] [PubMed] [Google Scholar]
  7. Ito Y.; Konoike T.; Saegusa T. Synthesis of 1,4-Diketones by the Reaction of Silyl Enol Ether with Silver Oxide. Regiospecific Formation of Silver(I) Enolate Intermediates. J. Am. Chem. Soc. 1975, 97, 649–651. 10.1021/ja00836a034. [DOI] [Google Scholar]
  8. Baciocchi E.; Casu A.; Ruzziconi R. Synthesis of Unsymmetrical 1,4-Diketones by the Ceric Ammonium Nitrate Promoted Cross-Coupling of Trimethylsilyl Enol Ethers. Tetrahedron Lett. 1989, 30, 3707–3710. 10.1016/S0040-4039(01)80489-5. [DOI] [Google Scholar]
  9. Fujii T.; Hirao T.; Ohshiro Y. Oxovanadium-Induced Oxidative Desilylation for the Selective Synthesis of 1,4-Diketones. Tetrahedron Lett. 1992, 33, 5823–5826. 10.1016/0040-4039(92)89041-A. [DOI] [Google Scholar]
  10. Schmittel M.; Burghart A.; Malisch W.; Reising J.; Söllner R. Diastereoselective Enolate Coupling through Redox Umpolung in Silicon and Titanium Bisenolates: A Novel Concept Based on Intramolecularization of Carbon–Carbon Bond Formation. J. Org. Chem. 1998, 63, 396–400. 10.1021/jo971650x. [DOI] [Google Scholar]
  11. a Avetta C. T.; Konkol L. C.; Taylor C. N.; Dugan K. C.; Stern C. L.; Thomson R. J. Diastereoselective Oxidative Carbon–Carbon Bond Formation via Silyl Bis-enol Ethers. Org. Lett. 2008, 10, 5621–5624. 10.1021/ol802516z. [DOI] [PubMed] [Google Scholar]; b Clift M. D.; Taylor C. N.; Thomson R. J. Oxidative Carbon–Carbon Bond Formation via Silyl Bis-enol Ethers: Controlled Cross-Coupling for the Synthesis of Quaternary Centers. Org. Lett. 2007, 9, 4667–4669. 10.1021/ol702306z. [DOI] [PubMed] [Google Scholar]
  12. Mizar P.; Wirth T. Flexible Stereoselective Functionalizations of Ketones through Umpolung with Hypervalent Iodine Reagents. Angew. Chem., Int. Ed. 2014, 53, 5993–5997. 10.1002/anie.201400405. [DOI] [PubMed] [Google Scholar]
  13. a Osafune Y.; Jin Y.; Hirao T.; Tobisu M.; Amaya T. Oxovanadium(v)-Catalyzed Oxidative Cross-Coupling of Enolates using O2 as a Terminal Oxidant. Chem. Commun. 2020, 56, 11697–11700. 10.1039/D0CC04395H. [DOI] [PubMed] [Google Scholar]; b Amaya T.; Osafune Y.; Maegawa Y.; Hirao T. Vanadium(V)-Induced Oxidative Cross-Coupling of Various Boron and Silyl Enolates. Chem. - Asian J. 2017, 12, 1301–1304. 10.1002/asia.201700470. [DOI] [PubMed] [Google Scholar]; c Amaya T.; Maegawa Y.; Masuda T.; Osafune Y.; Hirao T. Selective Intermolecular Oxidative Cross-Coupling of Enolates. J. Am. Chem. Soc. 2015, 137, 10072–10075. 10.1021/jacs.5b05058. [DOI] [PubMed] [Google Scholar]
  14. Parida K. N.; Pathe G. K.; Maksymenko S.; Szpilman A. M. Cross-Coupling of Dissimilar Ketone Enolates via Enolonium Species to afford Non-Symmetrical 1,4-Diketones. Beilstein. J. Org. Chem. 2018, 14, 992–997. 10.3762/bjoc.14.84. [DOI] [PMC free article] [PubMed] [Google Scholar]
  15. a Fang G.; Bi X. Silver-Catalysed Reactions of Alkynes: Recent Advances. Chem. Soc. Rev. 2015, 44, 8124–8173. 10.1039/C5CS00027K. [DOI] [PubMed] [Google Scholar]; b Weibel J.-M.; Blanc A.; Pale P. Ag-Mediated Reactions: Coupling and Heterocyclization Reactions. Chem. Rev. 2008, 108, 3149–3173. 10.1021/cr078365q. [DOI] [PubMed] [Google Scholar]
  16. Bi X.; Li C.-J.. Silver Catalysis in Organic Synthesis, Volumes 1 and 2; Wiley-VCH Verlag GmbH & Co. KGaA, 2019. [Google Scholar]
  17. a Capdevila L.; Andris E.; Briš A.; Tarrés M.; Roldán-Gómez S.; Roithová J.; Ribas X. Silver(I)-Catalyzed C–X, C–C, C–N, and C–O Cross-Couplings Using Aminoquinoline Directing Group via Elusive Aryl-Ag(III) Species. ACS Catal. 2018, 8, 10430–10436. 10.1021/acscatal.8b03257. [DOI] [Google Scholar]; b Font M.; Acuña-Parés F.; Parella T.; Serra J.; Luis J. M.; Lloret-Fillol J.; Costas M.; Ribas X. Direct Observation of Two-Electron Ag(I)/Ag(III) Redox Cycles in Coupling Catalysis. Nat. Commun. 2014, 5, 4373. 10.1038/ncomms5373. [DOI] [PubMed] [Google Scholar]
  18. Wu W.; Cui E.; Zhang Y.; Zhang C.; Zhu F.; Tung C.-H.; Wang Y. Involving Single-Atom Silver(0) in Selective Dehalogenation by AgF under Visible-Light Irradiation. ACS Catal. 2019, 9, 6335–6341. 10.1021/acscatal.9b01929. [DOI] [Google Scholar]
  19. a Chang M.-Y.; Cheng Y.-C.; Lu Y.-J. One-Pot Access to Sulfonylmethyl Arylpyrroles via the Domino Aerobic Wacker-Type Aminocyclization/1,4-Sulfonyl Migration. Org. Lett. 2014, 16, 6252–6255. 10.1021/ol5032238. [DOI] [PubMed] [Google Scholar]; b Zheng X.; Lu S.; Li Z. The Rearrangement of tert-Butylperoxides for the Construction of Polysubstituted Furans. Org. Lett. 2013, 15, 5432–5435. 10.1021/ol402509u. [DOI] [PubMed] [Google Scholar]
  20. Chudasama V.; Fitzmaurice R. J.; Caddick S. Hydroacylation of α,β-Unsaturated Esters via Aerobic C–H Activation. Nat. Chem. 2010, 2, 592–596. 10.1038/nchem.685. [DOI] [PubMed] [Google Scholar]
  21. Ni Z.; Zhang Q.; Xiong T.; Zheng Y.; Li Y.; Zhang H.; Zhang J.; Liu Q. Highly Regioselective Copper-Catalyzed Benzylic C–H Amination by N-Fluorobenzenesulfonimide. Angew. Chem., Int. Ed. 2012, 51, 1244–1247. 10.1002/anie.201107427. [DOI] [PubMed] [Google Scholar]
  22. a Wu H.; Wang Y.-C.; Shatskiy A.; Li Q.-Y.; Liu J.-Q.; Kärkäs M. D.; Wang X.-S. Modular Synthesis of 3-Substituted Isocoumarins via Silver-Catalyzed Aerobic Oxidation/6-endo Heterocyclization of ortho-Alkynylbenzaldehydes. Org. Biomol. Chem. 2021, 19, 6657–6664. 10.1039/D1OB01065D. [DOI] [PubMed] [Google Scholar]; b Liu J.; Liu Z.; Liao P.; Zhang L.; Tu T.; Bi X. Silver-Catalyzed Cross-Coupling of Isocyanides and Active Methylene Compounds by a Radical Process. Angew. Chem., Int. Ed. 2015, 54, 10618–10622. 10.1002/anie.201504254. [DOI] [PubMed] [Google Scholar]
  23. a Tang P.; Furuya T.; Ritter T. Silver-Catalyzed Late-Stage Fluorination. J. Am. Chem. Soc. 2010, 132, 12150–12154. 10.1021/ja105834t. [DOI] [PMC free article] [PubMed] [Google Scholar]; b Furuya T.; Strom A. E.; Ritter T. Silver-Mediated Fluorination of Functionalized Aryl Stannanes. J. Am. Chem. Soc. 2009, 131, 1662–1663. 10.1021/ja8086664. [DOI] [PubMed] [Google Scholar]

Associated Data

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

Supplementary Materials

ol2c01477_si_001.pdf (3.1MB, pdf)

Articles from Organic Letters are provided here courtesy of American Chemical Society

RESOURCES