New amino-, imino- and oxazolinophosphites based on 1,1′-bi-2-naphtol: coordination and catalytic properties

A series of the new chiral BINOL-based phosphite P,N-hybrid ligands was prepared. The coordination behavior of all the ligands was studied and the neutral complexes [Rh(CO)Cl(P∧N)] were synthesized in order to characterize a degree of the electronic non-symmetry of donating centers. Also the neutral and cationic complexes cis-[PdCl2(η2-P∧N)], cis-[PdCl2(η1-P∧N)2], cis-[PdCl(η2-P∧N)(η1-P∧N)]+Cl−, [Pd(allyl)(η2-P∧N)]+X− (X−=Cl−, BF4−) were obtained and characterized. The new P,N-hydrid ligands gave up to 81% ee in the enantioselective Pd-catalyzed alkylation of 3-penten-2-yl carbonate by dimethyl malonate and up to 60% ee in the Rh-catalyzed hydrosilylation of acetophenone and acetylferrocene by diphenylsilane.