Applications of 4,4‘-(Me₃Si)₂-BINAP in Transition-Metal-Catalyzed Asymmetric Carbon−Carbon Bond-Forming Reactions

A recently developed BINAP derivative with trimethylsilyl substituents on the 4- and 4‘-positions of the binaphthyl skeleton, 2,2‘-bis(diphenylphosphino)-4,4‘-bis(trimethylsilyl)-1,1‘-binaphthyl (tms-BINAP), was used in a variety of transition-metal-catalyzed asymmetric carbon−carbon bond-forming reactions. In π-allylpalladium-mediated reactions, tms-BINAP gave better enantioselectivity than the unsubstituted BINAP, and the origin of the improved enantioselectivity was gained from an X-ray structural study of [Pd(η3-C3H5)((R)-tms-BINAP)]ClO4.