Zn(II)-Stabilized Azo-Anion Radical-Catalyzed Dehydrogenative Synthesis of Olefins

Abstract

Herein, we describe a Zn-catalyzed atom-economical, inexpensive, and sustainable method for preparing a broad spectrum of substituted olefins utilizing alcohols as the main precursor. Using a Zn(II) complex [ZnLCl₂] (1) of the redox-noninnocent ligand 2-((4-chlorophenyl)diazenyl)-1,10-phenanthroline (L), various (E)-olefins were prepared in good yields by coupling alcohols with sulfones and aryl cyanides under an inert atmosphere. Under an aerial atmosphere, vinyl nitriles were isolated in up to 82% yield reacting alcohols with benzyl cyanides in the presence of 1. Control experiments and mechanistic investigation indicate the active involvement of the aryl-azo ligand as an electron and hydrogen reservoir, permitting 1 to perform as a promising catalyst.