Oxidative Cleavage and Fluoromethylthiolation of C═C Bonds: A General Route toward Mono-, Di-, and Trifluoromethylthioesters from Alkenes

Abstract

A novel oxidative cleavage and fluoromethylthiolation reaction of C�C bonds has been developed that represents the first and general method for the preparation of mono-, di-, and trifluoromethylthioesters from alkenes. The protocol features excellent product selectivity and substrate suitability. Various observations suggested that the protocol proceeded via a two-step radical process and that aldehyde was the key intermediate. What's more meaningful is that this route provides a new direction for converting alkenes into higher-value-added carbonyl-containing chemicals.

Direct Synthesis of Monofluoromethylthioesters from Acyl Chlorides with Elemental Sulfur and Fluoroiodomethane

“…[11,12] Therefore, these methods suffer from some limitations, such as unpleasant odors, narrow substrate scopes and harsh reaction conditions. More recent approaches involve direct monofluoromethylthiolation of alkenes [13] or aldehydes [14] with an electrophilic monofluoromethylthiolating reagent (PhSO 2 SCH 2 F) (Scheme 1c). Although sulfur-containing substrates are no longer necessary, the monofluoromethylthiolating reagent still needs to be prepared in advance, which limits the practicality of these methods to some extent.…”