Homo‐ and Cross‐Olefin Metathesis Coupling of Vinylphosphane Oxides and Electron‐Poor Alkenes: Access to P‐Stereogenic Dienophiles

Abstract

Abstract Vinylphosphane oxides 6 undergo catalytic olefin homo‐metathesis leading to achiral and P‐stereogenic diphosphane dioxides 7 with exclusive ( E )‐selectivity. Similarly, EWG‐substituted vinylphosphane oxides 11, 12 could be prepared with complete ( E )‐olefin selectivity via olefin cross‐metathesis with electron‐deficient substrates, such as methyl acrylate and 2‐fluorostyrene, using nitro‐Hoveyda ruthenium precatalyst III . Cross‐ and homo‐metathesis of chiral non‐racemic vinylphosphane oxides proceeds without racemization of the phosphorus center of chirality.