Radical Fluoroalkylation of Isocyanides with Fluorinated Sulfones by Visible‐Light Photoredox Catalysis

Rong, Jian; Deng, Linhua; Tan, Peng; Ni, Chuanfa; Gu, Yu‐Cheng; Hu, Jinbo

doi:10.1002/anie.201510533

Cited by 323 publications

(156 citation statements)

References 64 publications

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“…Due to its membrane permeability, difluoromethyl group (CF 2 R) is routinely employed in search for lead structures in drug discovery in recent years16, and has thus inspired the development of new reagents and strategies for the synthesis of difluoromethyl-containing compounds49505152535455565758. However, there are very few catalytic asymmetric approaches to access such chiral building blocks containing difluoromethyl groups, using a direct fluoroalkylation strategy58.…”

Section: Resultsmentioning

confidence: 99%

Catalytic asymmetric radical aminoperfluoroalkylation and aminodifluoromethylation of alkenes to versatile enantioenriched-fluoroalkyl amines

et al. 2017

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Although great success has been achieved in asymmetric fluoroalkylation reactions via nucleophilic or electrophilic processes, the development of asymmetric radical versions of this type of reactions remains a formidable challenge because of the involvement of highly reactive radical species. Here we report a catalytic asymmetric radical aminoperfluoroalkylation and aminodifluoromethylation of alkenes with commercially available fluoroalkylsulfonyl chlorides as the radical sources, providing a versatile platform to access four types of enantioenriched α-tertiary pyrrolidines bearing β-perfluorobutanyl, trifluoromethyl, difluoroacetyl and even difluoromethyl groups in excellent yields and with excellent enantioselectivity. The key to success is not only the introduction of the CuBr/chiral phosphoric acid dual-catalytic system but also the use of silver carbonate to suppress strong background and side hydroamination reactions caused by a stoichiometric amount of the in situ generated HCl. Broad substrate scope, excellent functional group tolerance and versatile functionalization of the products make this approach very practical and attractive.

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Section: Resultsmentioning

confidence: 99%

Catalytic asymmetric radical aminoperfluoroalkylation and aminodifluoromethylation of alkenes to versatile enantioenriched-fluoroalkyl amines

et al. 2017

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“…Although there are severall iterature methodsf or conducting the S-trifluoromethylation of MBT, [8] we found that intermediate compound 1 could be most efficiently generated starting from the disulfide dimer MBTS through an in-house-developed photoredox catalysis method. Ar eactive reagent is only generated in the second step with simple methylation of the benzothiazole ring nitrogen with MeOTfa ffording BT-SCF 3 .…”

mentioning

confidence: 89%

Deoxytrifluoromethylthiolation and Selenylation of Alcohols by Using Benzothiazolium Reagents

Dix

Jakob

Hopkinson

2019

Chemistry A European J

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Aliphatic compounds substituted with medicinally importantt rifluoromethylthio (SCF 3 )a nd trifluoromethylselenyl (SeCF 3 )g roups weres ynthesized directly from alcohols by using the new benzothiazolium salts BT-SCF 3 and BT-SeCF 3 .T hese bench-stable fluorine-containing reagents are facile to use and can be prepared in two steps from non-fluorinated heteroaromatic startingm aterials. The metal-free deoxytrifluoromethylthiolation process using BT-SCF 3 proceeds under mild conditions and the similarly efficient trifluoromethylselenylationr eactions using BT-SeCF 3 are, to the besto fo ur knowledge, the first reported examples of this transformation.Scheme1.a) Benzothiazolium Reagents BT-SCF 3 and BT-SeCF 3 .b )Previously reported deoxytrifluoromethylthiolation reactionso fa liphatic alcohols. c) This work: Deoxytrifluoromethylthiolation and selenylation of alcohols with BT-SCF 3 and BT-SeCF 3 .[bmim] = 1-Butyl-3-methylimidazolium.[a] S.Scheme2.a) Two-step synthesisofBT-SCF 3 and its applicationi nthe deoxytrifluoromethylthiolation of aliphatic alcohol 2a.b)Likely reaction mechanism via 2-alkoxybenzothiazolium salt 4.

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“…The direct difluoromethylation of isocyanides with a new CF 2 precursor 2h in the presence of [Ru(bpy) 3 ]Cl 2 ·•6H 2 O was developed by Hu and co--workers (Scheme 57). 71 Heterocyclic groups and SO 2 Me were tolerated under the conditions. This method also provided the application of a variety of mono-and trifluoromethyl heteroarylsulfones as the radical fluoroalkylation sources.…”

Section: Direct Difluoromethylation With Hcf 2 Lgmentioning

confidence: 99%

Recent advances in photoinduced trifluoromethylation and difluoroalkylation

2016

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Recent advances of photoinduced trifluoromethylation and difluoroalkylation under photocatalysis are summarized. Most of photoredox reactions proceed efficiently under mild condition with simple operation. Various fluorinated reagents are developed and applied in different transformations. Usually, the photocatalyst in photocatalytic cycle is initially stimulated to the exited state in the presence of visible light, which then provides an electron to the fluorinated reagent to release CF3 radical or CF2 radical. The subsequent radical addition to unsaturated bond with further transformations would produce the corresponding fluorinated products. Alkenes, alkynes, isocyanides, and arenes are frequently employed as substrates for access to fluorochemicals. The advantages of trifluoromethylation and difluoroalkylation under photocatalysis including mild reaction conditions, good functional group tolerance, and experimental ease will make the approaches attractive for further applications. Organic Chemistry Frontiers Journal Name REVIEW This journal is Journal Name REVIEW This journal is Journal Name REVIEW This journal is Journal Name REVIEW This journal is Journal Name REVIEW This journal is Journal Name REVIEW This journal is Journal Name REVIEW This journal is Journal Name REVIEW This journal is

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Radical Fluoroalkylation of Isocyanides with Fluorinated Sulfones by Visible‐Light Photoredox Catalysis

Cited by 323 publications

References 64 publications

Catalytic asymmetric radical aminoperfluoroalkylation and aminodifluoromethylation of alkenes to versatile enantioenriched-fluoroalkyl amines

Catalytic asymmetric radical aminoperfluoroalkylation and aminodifluoromethylation of alkenes to versatile enantioenriched-fluoroalkyl amines

Deoxytrifluoromethylthiolation and Selenylation of Alcohols by Using Benzothiazolium Reagents

Recent advances in photoinduced trifluoromethylation and difluoroalkylation

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