Fluoroalkanesulfinate Salts as Dual Fluoroalkyl and SO<sub>2</sub> Sources: Atom-Economical Fluoroalkyl-Sulfonylation of Alkenes and Alkynes by Photoredox Catalysis

Tanaka, Seiya; Nakayama, Yuushou; Konishi, Yusuke; Koike, Takashi; Akita, Munetaka

doi:10.1021/acs.orglett.0c00789

Cited by 31 publications

(17 citation statements)

References 57 publications

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“…However, our proposed strategy faced several challenges. First of all, there are only scarce examples of single-electron-transfer (SET) reduction of the newly generated carbon radicals in GTRA reactions, which typically undergo direct couplings or oxidation to carbon cations instead . Second, in comparison to common carboxylations with high pressure and/or high excesses of CO 2 , it is challenging to realize efficient carboxylations via C–C bond formation with the (sub)stoichiometric amounts and low concentrations of CO 2 inherent to the proposed catalytic conditions. , Moreover, the proposed nucleophilic carbanions also would be generated catalytically in low concentrations and they could undergo undesired side reactions, such as protonation, instead of the desired carboxylation.…”

Section: Introductionmentioning

confidence: 99%

α-Amino Acids and Peptides as Bifunctional Reagents: Carbocarboxylation of Activated Alkenes via Recycling CO₂

et al. 2021

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Carboxylic acids, including amino acids (AAs), have been widely used as reagents for decarboxylative couplings. In contrast to previous decarboxylative couplings that release CO 2 as a waste byproduct, herein we report a novel strategy with simultaneous utilization of both the alkyl and carboxyl components from carboxylic acids. Under this unique strategy, carboxylic acids act as bifunctional reagents in the redox-neutral carbocarboxylation of alkenes. Diverse, inexpensive, and readily available α-AAs take part in such difunctionalizations of activated alkenes via visiblelight photoredox catalysis, affording a variety of valuable but otherwise difficult to access γ-aminobutyric acid derivatives (GABAs). Additionally, a series of dipeptides and tripeptides also participate in this photocatalytic carbocarboxylation. Although several challenges exist in this system due to the low concentration and quantitative amount of CO 2 , as well as unproductive side reactions such as hydrodecarboxylation of the carboxylic acids and hydroalkylation of the alkenes, excellent regioselectivity and moderate to high chemoselectivity are achieved. This process features low catalyst loading, mild reaction conditions, high step and atom economy, and good functional group tolerance, and it is readily scalable. The resulting products are subject to efficient derivations, and the overall process is amenable to applications in the latestage modification of complex compounds. Mechanistic studies indicate that a carbanion is generated catalytically and it acts as the key intermediate to react with CO 2 , which is also generated catalytically in situ and thus remains in low concentration. The overall transformation represents an efficient and sustainable system for organic synthesis, pharmaceutics, and biochemistry.

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Section: Introductionmentioning

confidence: 99%

α-Amino Acids and Peptides as Bifunctional Reagents: Carbocarboxylation of Activated Alkenes via Recycling CO₂

et al. 2021

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“…Using these reagents, many research groups have achieved various difunctional modifications of the styrenes and unactivated alkenes through trifluoromethyl radicals. These research results can be divided into carbo‐CF 3 , [15] amino‐CF 3 , [16] oxo‐CF 3 , [17] thio‐CF 3 , [18] halo‐CF 3 [19] . and so on.…”

Section: Methodsmentioning

confidence: 99%

Visible‐Light‐Induced Three‐Component Intermolecular Trifluoromethyl‐Alkenylation Reactions of Unactivated Alkenes

et al. 2021

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Herein, we describe a practical protocol for efficient, mild, visible‐light‐induced three‐component intermolecular trifluoromethyl‐alkenylation reactions of unactivated alkenes. The protocol has good functional group tolerance and a broad substrate scope. Using this protocol, we not only introduced a trifluoromethyl group into alkenes but also converted unactivated alkenes to styrene‐based activated alkenes, in addition to accomplishing late‐stage functionalization of pharmaceutical intermediates.

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“…Alkenes and alkynes react with Langlois’ reagent in the presence of Ir photocatyst ([Ir{dF(CF 3 )ppy} 2 (bpy)](PF 6 )]) and DMSO as solvent and irradiation of blue LED (Scheme 13). [55] …”

Section: Application Of Langlois’ Reagent In Organic Transformationsmentioning

confidence: 99%

Recent Advances on the Application of Langlois’ Reagent in Organic Transformations

et al. 2021

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Langlois’ reagent (trifluoromethanesulfinate salt) has been proven to be a valuable reagent for the synthesis of various classes of molecules, mainly trifluoromethylated compounds, in academic, biological and industrial research. Synthetic uses of Langlois’ reagent in organic transformations of aromatic and heteroaromatic compounds, alkenes, alkynes, boronic acids, carboxylic acids, and etc are discussed.This review aims to demonstrate the ongoing utility of Langlois’ reagent in the preparation of various classes of organic compounds. Furthermore, to address the recent collective papers, the current review summarizes and comprehensively describes manuscripts on synthetic applications of Langlois’ reagent since 2015 until today.

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Fluoroalkanesulfinate Salts as Dual Fluoroalkyl and SO₂ Sources: Atom-Economical Fluoroalkyl-Sulfonylation of Alkenes and Alkynes by Photoredox Catalysis

Cited by 31 publications

References 57 publications

α-Amino Acids and Peptides as Bifunctional Reagents: Carbocarboxylation of Activated Alkenes via Recycling CO₂

α-Amino Acids and Peptides as Bifunctional Reagents: Carbocarboxylation of Activated Alkenes via Recycling CO₂

Visible‐Light‐Induced Three‐Component Intermolecular Trifluoromethyl‐Alkenylation Reactions of Unactivated Alkenes

Recent Advances on the Application of Langlois’ Reagent in Organic Transformations

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Fluoroalkanesulfinate Salts as Dual Fluoroalkyl and SO2 Sources: Atom-Economical Fluoroalkyl-Sulfonylation of Alkenes and Alkynes by Photoredox Catalysis

Cited by 31 publications

References 57 publications

α-Amino Acids and Peptides as Bifunctional Reagents: Carbocarboxylation of Activated Alkenes via Recycling CO2

α-Amino Acids and Peptides as Bifunctional Reagents: Carbocarboxylation of Activated Alkenes via Recycling CO2

Visible‐Light‐Induced Three‐Component Intermolecular Trifluoromethyl‐Alkenylation Reactions of Unactivated Alkenes

Recent Advances on the Application of Langlois’ Reagent in Organic Transformations

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Product

Resources

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Fluoroalkanesulfinate Salts as Dual Fluoroalkyl and SO₂ Sources: Atom-Economical Fluoroalkyl-Sulfonylation of Alkenes and Alkynes by Photoredox Catalysis

α-Amino Acids and Peptides as Bifunctional Reagents: Carbocarboxylation of Activated Alkenes via Recycling CO₂

α-Amino Acids and Peptides as Bifunctional Reagents: Carbocarboxylation of Activated Alkenes via Recycling CO₂