Electrochemical heterodifunctionalization of α-CF₃alkenes to access α-trifluoromethyl-β-sulfonyl tertiary alcohols

Abstract

An unprecedented electrochemical heterodifunctionalization of α-CF3 alkenes with benzenesulfonyl hydrazides was accomplished in this work, wherein a β-sulfonyl and a α-hydroxyl group were simultaneously incorporated across the olefinic double bond...

Electrochemical‐Induced Hydroxysulfonylation of α‐CF3 Alkenes to Access Tertiary β‐Hydroxysulfones

“…Based on the above experiments and previous reports, [18] a proposed mechanism was described in Scheme 6. Firstly, sodium sulfinate was oxidized at the anode to produce sulfonyl radical I .…”

“…This observation demonstrated the occurrence of hydrogen production at the cathode. At last, when H 2 18O was added instead of H 2 O to the template substrate, 18 O-labelling product 6 was detected (Scheme 5, see supporting information for details, Scheme S9). This result indicated that the OH group of the target product was derived from water.…”

“…Meanwhile, KI is essential for the good chemical yield. [16] Compared with sulfonyl hydrazides used in Yang's work, sodium sulfinates are cheaper, non-toxic, odorless, stable, and easy-toprepare sulfonylating agents with diverse reactivity. [17] Herein, we successfully established the hydroxysulfonylation of α-CF 3 -alkenes to form α-CF 3 -substituted tertiary alcohols by using sodium sulfinates via a green electrochemical method (Scheme 2c).…”

Multicomponent reactions and photo/electrochemistry join forces: atom economy meets energy efficiency

“…In 2021 Ye et al reported an alternative route toward bhydroxysulfones, employing sulfonyl hydrazide as the Scentered radical source in electrocatalytic conditions. 95 The activation of sulfonyl hydrazides can occur by the direct oxidation at the anode; nonetheless, a significant increment in the yield upon the addition of KI suggested an additional mechanism involving a series of HAT from the hydrazide to anodically formed iodine radicals, resulting in the elimination of nitrogen and formation of the sulfonyl radical. The usual radical attack/ mechanism sequence then leads to the formation of a benzyl cation trapped by a hydroxide anion formed at the cathode.…”

Tunable photocatalytic oxysulfonylation and chlorosulfonylation of α-CF3 alkenes with sulfonyl chlorides

“…Very recently, Yang and his colleagues reported a visible-light-induced sulfonation of α-trifluoromethylstyrenes with sodium sulfinates 7 and electrochemical sulfonation of α-trifluoromethylstyrenes with benzenesulfonyl hydrazides. 8 They successfully accomplished heterodifunctionalization of α-CF 3 alkenes for the first time, affording α-trifluoromethyl-β-sulfonyl tertiary alcohols. In these works, the sulfonyl radicals were generated from benzenesulfonyl hydrazides and sodium benzenesulfinates, which were derivatized from commercially available sulfonyl chloride.…”