Application of P‐Bridged Biaryl Phosphines in Pd‐Catalyzed α‐Arylation Reactions

The use of catalysts derived from Pd2(dba)3 and phosphatrioxa‐adamantane framework (Cg) has been demonstrated to facilitate the effective alpha(α)‐arylation of ketones using a diverse array of aryl halides under mild reaction conditions (40 °C–80 °C). The evaluation of phosphines with dissimilar stereoelectronic properties revealed the pivotal role of fine‐tuning the ligand's steric bulk. In particular, catalysts based on the Cg‐biphenyl ligand (1) proved efficient for facile α‐arylation of electronically and sterically diverse aryl bromides and chlorides. The structure‐activity relationship of a small array of P‐bridged biaryl phosphines using structurally diverse aryl bromides and chlorides was investigated in Pd‐catalyzed α‐arylation of ketones reactions.