NHC-Catalyzed Metathesis and Phosphorylation Reactions of Disulfides: Development and Mechanistic Insights

Abstract

The development of efficient methods for the metathesis and phosphorylation reactions of disulfide compounds is of widespread interest due to their important synthetic utility in polymer, biological, medicinal and agricultural chemistry. Herein, we demonstrate the use of N-heterocyclic carbenes (NHCs) as versatile organocatalysts to promote these challenging reactions under mild conditions. This metal- and oxidant-free protocol is operationally simple with very short reaction times. The interplay between the nucleophilicity and basicity of NHCs in these reactions were also elucidated by NMR studies and high-level ab initio calculations.

Keywords: carbenes; disulfide; high-level ab initio calculations; organocatalysis; phosphorylation.