Alkenyl Thioetherification Enabled by Nickel Catalysis

Abstract

This paper describes an efficient strategy to promote alkenyl thioetherifications via the Ni-catalyzed cross-coupling of inactivated or β-aryl-substituted (E)-alkenyl halides with thio-alcohols/phenols. The present strategy with easy-to-operate reaction conditions represents one of the most effective alkenyl C(sp2)–S bond-forming methods via readily accessible nickel catalysis. Notably, the mildly basic conditions employed facilitate access to a broad scope including protected amino acids, saccharides, and heterocycles. Moreover, this work presents its attractive usefulness by the application in late-stage modifications of several structurally complex natural products and pharmaceuticals.

Polyoxometalate-based ionic liquids: efficient reversible phase transformation-type catalysts for thiolation of alcohols to construct C–S bonds

“…To date, a series of methods have been developed for the synthesis of thioethers, including the traditional nucleophilic substitution of alkyl halides with thiols under basic conditions, 11,12 the cross-coupling reaction of thiols with halides, aryl boronic acids, alcohols or esters, 13–17 and hydrothiolation of alkynes catalyzed by transition metals and so on. 18 As easily available and cheap sources of electrophiles, alcohols become attractive candidates to react with thiols for the construction of C–S bonds and these reactions are commonly atom-efficient generating water as the only by-product.…”