Highly (<i>E</i>)-Selective Trisubstituted Alkene Synthesis by Low-Valent Titanium-Mediated Homolytic Cleavage of Alcohol C–O Bond

Abstract

Ti-mediated homolytic C–O bond cleavage was useful for cascade radical–ionic reactions. Benzyl alcohols treated with TiCl4(col) (col = 2,4,6-collidine) and Mn powder generated the corresponding benzyl radicals; in addition, their reaction with 2-carboxyallyl acetates and the subsequent elimination of the acetoxy group yielded α,β-unsaturated carbonyl compounds with exclusive (E)-stereoselectivity. The simplicity of the procedure and its wide substrate scope represent a solution to the drawbacks associated with the reactions.