For the first time, the synthesis of thioesters starting from enals and thiols has been performed in the presence of a bulky N-heterocyclic carbene (NHC) as a catalyst.

The first metal-free protocol for efficient synthesis of unsymmetric bis(thioesters) via functionalization of dithiols with two different α,β-unsaturated aldehydes is presented.

A new simple, metal-free modification of mercapto-substituted silsesquioxane (SQ-SH) with α,β-unsaturated aldehydes is presented.