Modular synthesis of divergent thiofunctionalized sulfoxonium ylides†

Abstract

A metal-free protocol for the modular synthesis of diverse α-thiofunctionalized-α′-carbonyl sulfoxonium ylides from sulfoxonium–iodonium hybrid ylides (I^(III)/S^(VI)-ylides) has been achieved. Three types of sulfur-containing functional groups including –SC(S)–NR¹R², –SAr and –SNR can be easily installed at the α-position of sulfoxonium ylides, delivering dithiocarbamation, thiolation and sulfilimination products with an extremely broad scope (up to 122 examples). Notably, the new α-thiofunctionalized sulfoxonium ylides were readily converted into high value-added gem-difunctionalized ketones. Furthermore, density functional theory (DFT) calculations for the proposed mechanism were also demonstrated. This method offers a powerful and significant platform for the modular construction of thiofunctionalized sulfoxonium ylides and gem-difunctionalized ketones in synthetic and medicinal chemistry.