Radical-mediated reduction of the dithiocarbamate group under tin-free conditions.

Abstract

Reductive desulfurisation of dithiocarbamates is conveniently achieved using H(3)PO(2)-Et(3)N-ACCN in refluxing dioxane. Fused and spirocyclic β-lactams, prepared through 4-exo trig carbamoyl radical cyclisation-dithiocarbamate group transfer reactions, are reduced without fragmentation of the strained 4-membered ring. Diethyl tetraacetyl-d-glucopyranosyl dithiocarbamate is selectively reduced with or without acyloxy group migration depending on reaction conditions and choice of reductant. Deuterium incorporation from D(3)PO(2)-Et(3)N is observed for a system involving a nucleophilic radical intermediate, but not in the case of the electrophilic radical obtained through acyloxy group migration on a glucose derivative.

DOI: 10.1039/c2ob25434d

Cite this paper

@article{McMaster2012RadicalmediatedRO, title={Radical-mediated reduction of the dithiocarbamate group under tin-free conditions.}, author={Claire McMaster and Robert N Bream and Richard S Grainger}, journal={Organic & biomolecular chemistry}, year={2012}, volume={10 24}, pages={4752-8} }