Manganese‐Catalyzed Three‐Component Vinylation of Phosphines with Sulfones and Alcohols

Abstract Herein, we report a manganese‐catalyzed three‐component vinylation strategy for the synthesis of vinylphosphines from readily available alcohols, sulfones, and phosphines via acceptorless dehydrogenative strategy. This multi‐component, four‐stage, one‐pot protocol offers a stereoselective approach, overcoming the challenges associated with achieving these products through the hydrophosphination of terminal alkynes. The reaction utilizes sulfones and common alcohols to access both ( E )‐ β ‐substituted vinylphosphines (using methanol) and α ‐substituted vinylphosphines (using primary alcohols) in yields ranging from 52% to 99%, with E : Z stereoselectivity of 95:5 to 99:1. Importantly, the synthesized branched‐substituted vinylphosphines exhibited superior ligand performance in the copper‐catalyzed cross‐coupling of aryl bromides with pyrazole compared to the commercially available PPh 3 and diphenyl(vinyl)phosphane.