Radical Silyldifluoromethylation of Electron-Deficient Alkenes

Supranovich, Vyacheslav I.; Levin, Vitalij V.; Стручкова, Марина И.; Korlyukov, Alexander A.; Dilman, Alexander D.

doi:10.1021/acs.orglett.7b01334

Cited by 52 publications

(28 citation statements)

References 52 publications

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“…Modern synthetic methods are beginning to emerge for the preparation of complex substituted difluoroalkyl organosilanes, which will undergo addition to aldehydes. Examples include Dilman's radical‐mediated photochemical addition of a difluorosilyl radical to electron deficient alkenes to give complex carbonyl‐containing difluoroalkylsilane 46 , and Mikami's defluorinative difluorosilylation of lithium enolates using Me 3 SiCF 3 to give 48 . Both of these complex difluoroalkylsilanes undergo addition to aldehydes under similar fluoride‐mediated conditions to give difluoroalkyl alcohols 47 and 49 .…”

Section: Synthesis Of Difluoroketones By a Fluorinated‐building‐blmentioning

confidence: 99%

Methods for the Synthesis of α,α‐Difluoroketones

Pattison

2018

Eur J Org Chem

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α,α‐Difluoroketones are valuable compounds and can be used as synthetic intermediates for the synthesis of fluorinated molecules, but they also have a direct application in medicinal chemistry, particularly as inhibitors for hydrolytic enzymes. This Microreview will summarize the major methods currently available for the synthesis of α,α‐difluoroketones, highlighting methods involving direct C–F bond formation, as well as those using pre‐difluorinated building blocks.

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Section: Synthesis Of Difluoroketones By a Fluorinated‐building‐blmentioning

confidence: 99%

Methods for the Synthesis of α,α‐Difluoroketones

Pattison

2018

Eur J Org Chem

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“…This silane is very sensitive to Lewis bases and accordingly it was used as a precursor of difluorocarbene, which can react with enol ethers [ 19 – 20 ] ( Scheme 1 ). We showed that this silane could be involved in the radical chain hydrofluoroalkylation of electron-deficient alkenes, using a boron hydride as a source of hydrogen [ 21 ]. We thought that silane 1 could couple with silyl enol ethers in the presence of a photocatalyst affording fluoroalkylation products.…”

Section: Resultsmentioning

confidence: 99%

Photoredox-catalyzed silyldifluoromethylation of silyl enol ethers

Supranovich

Levin

Dilman

2020

Beilstein J. Org. Chem.

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A method for the light-mediated fluoroalkylation of silyl enol ethers with (bromodifluoromethyl)trimethylsilane followed by a reduction of the primary products with sodium borohydride is described. An 18 W, 375 nm LED was used as the light source. The reaction is performed in the presence of a gold photocatalyst, which effects the generation of a (trimethylsilyl)difluoromethyl radical via cleavage of the carbon–bromine bond.

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“…In 2017, the Dilman group reported a radical silyldifluoromethylation of electron-deficient alkenes 237 assisted by an NHC•borane complex affording the silyldifluoroalkanes 239 in moderate to high yields (Scheme 97). 67 A wide range of electron-deficient alkenes with useful functional groups were suitable for this transformation. Control experiments with a light/dark sequence indicated a possible mechanism involving a radical chain pathway.…”

Section: Syn Thesismentioning

confidence: 99%

Visible-Light-Driven Organic Photochemical Reactions in the Absence of External Photocatalysts

et al. 2019

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Visible-light-driven organic photochemical reactions have attracted substantial attention from the synthetic community. Typically, catalytic quantities of photosensitizers, such as transition metal complexes, organic dyes, or inorganic semiconductors, are necessary to absorb visible light and trigger subsequent organic transformations. Recently, in contrast to these photocatalytic processes, a variety of photocatalyst-free organic photochemical transformations have been exploited for the efficient formation of carbon–carbon and carbon–heteroatom bonds. In addition to not requiring additional photocatalysts, they employ low-energy visible light irradiation, have mild reaction conditions, and enable broad substrate diversity and functional group tolerance. This review will focus on a summary of representative work in this field in terms of different photoexcitation modes.1 Introduction2 Visible Light Photoexcitation of a Single Substrate3 Visible Light Photoexcitation of Reaction Intermediates4 Visible Light Photoexcitation of EDA Complexes between Substrates5 Visible Light Photoexcitation of EDA Complexes between Substrates and Reaction Intermediates6 Visible Light Photoexcitation of Products7 Conclusion and Outlook

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Radical Silyldifluoromethylation of Electron-Deficient Alkenes

Cited by 52 publications

References 52 publications

Methods for the Synthesis of α,α‐Difluoroketones

Methods for the Synthesis of α,α‐Difluoroketones

Photoredox-catalyzed silyldifluoromethylation of silyl enol ethers

Visible-Light-Driven Organic Photochemical Reactions in the Absence of External Photocatalysts

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