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

Abstract

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.

Recent advances in the application of Langlois’ reagent in olefin difunctionalization

“…5 Kaboudin and co-workers highlighted Langlois’ reagent in terms of its reactivity and important applications. 6 Our group summarized the application of Langlois’ reagent in C–H functionalisation. 7 However, to the best of our knowledge, a recent overview to emphasize the difunctionalization of alkenes using Langlois’ reagent systematically is lacking.…”

Black Phosphorus Quantum Dots/Carbon Nitride-Reduced Graphene Oxide Ternary Heterojunction as a Multifunctional Metal-Free Photocatalyst for Photooxidation Reactions

“…53 After the introduction of electrophilic trifluoromethyl radical ( • CF 3 ) into electron-rich arenes by Langlois' group, many approaches have been investigated for producing high-value molecules containing the Fluor moiety. 54 Albeit the so-called Langlois reagent (CF 3 SO 2 Na) can be used as the source of many species for multipurpose, 55 the formation of • CF 3 requires single-electron oxidation. Not only to confirm the nonclassical heterojunction type-II of BPQDs/CN-rGO but also to generate the essential CF 3 -substituted organic molecules, Langlois reagent with high oxidation potential (+1.34 V vs NHE) was chosen.…”

Primary and Secondary Amines by Flavin‐Photocatalyzed Consecutive Desulfonylation and Dealkylation of Sulfonamides

“…At that moment, excited dAll * acts as a single electron oxidant to the co‐formed sulfinate. The resulting triflyl or nonaflyl radicals are known to fragment and form perfluoroalkyl radicals by SO 2 release (Scheme 7B) [57] . The perfluoroalkyl radical subsequently abstracts a hydrogen atom [58,59] from the alkyl group of the aniline generating a α‐aminoalkyl radical, which is oxidized by electron transfer to dAll * .…”

“…The resulting triflyl or nonaflyl radicals are known to fragment and form perfluoroalkyl radicals by SO 2 release (Scheme 7B). [57] The perfluoroalkyl radical subsequently abstracts a hydrogen atom [58,59] from the alkyl group of the aniline generating a α-aminoalkyl radical, which is oxidized by electron transfer to dAll*. The formed iminium salt is subsequently hydrolyzed to the corresponding aldehyde, which was detected by NMR spectroscopy and MS spectrometry in the reaction mixtures.…”