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

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 PPh₃ and diphenyl(vinyl)phosphane.