Regio- and stereospecific thiol-thioalkyne reaction facilitated by organic base

Abstract

As an indispensable part of click chemistry, thiol-yne reactions are of great importance in organic and material synthesis. Nevertheless, efficient strategies for the addition of thiols onto internal alkynes with excellent regio- and stereocontrol are still scarce. Here we report the regio- and stereospecific hydrothiolation of electron-rich thioalkynes facilitated by organic base additive, which could proceed exceedingly fast under ambient atmosphere and room temperature, affording beta trans addition products in up to nearly quantitative yields. The dual nature of sulfur atom in attracting and donating electrons is supposed to be pivotal in determining the regio- and stereospecificity. This system tolerates a wide scope of thiols and thioalkynes, and shows great potential in polymer synthesis. In combination of its excellent performance in diverse environmentally benign solvents, especially in water/dimethyl sulfoxide mixtures that are usually used in bio-related research, applications of this newly established click reaction in diverse fields are highly expected.