Base dependent 1,3-dithioacetals rearrangement over sulfoxidation under visible-light photocatalysis to access disulfide-linked-dithioesters

18 October 2021, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

Base dependent oxidative rearrangement of dithiolanes and dithianes to access disulfide-linked-dithioesters under visible-light photoredox catalytic conditions has been disclosed. The protocol demonstrated the ability to synthesize either rearranged product or sulfoxide by simply switching the base with inherent ability to make hydrogen bonding with sulfur atom. Unlike, the usual deprotection of thioacetals to corresponding aldehydes under the oxidative conditions, we observed the unique regioselective oxidative reactivity of thioacetals to form disulfide-linked-dithioester or sulfoxides. The generality of the protocol has been demonstrated by exploring a wide range of substrates. As an application the in-situ generated thyil radical has been trapped with disulfides to prepare hetro-disulfides of potential utility. The protocol proved to be practical on gram scale quantity and relied on clean energy source for the transformation. Based on the series of control experiments, cyclic volametry and Stern-Volmer studies the plausible mechanism has been proposed.

Keywords

Disulfide-linked dithioester
Regioselective oxidation
thioacetal rearrangement
photoredox catalysis
C-S bond cleavage

Supplementary materials

Title
Description
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Title
Base dependent 1,3-dithioacetals rearrangement over sulfoxidation under visible-light photocatalysis to access disulfide-linked-dithioesters
Description
This ESI contains the details of optimisation, general procedures, control experiments, mechanistic studies, characterisation data and copies of proton, carnon and fluorine NMR spectra
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