title: A new atropisomeric P,N ligand for rhodium-catalyzed asymmetric hydroboration.
abstract: A new optically active and large dihedral angle atropisomeric P,N ligand, pyphos, which contains a tertiary phosphine and pyridine moiety, was prepared and resolved through diastereomeric complexation with chiral palladium amine complexes. The hexafluorophosphate salt of the diastereomers were found to be separable by fractional recyrstallization, while the corresponding chloride salt did not. [Rh(COD)pyphos]PF(6) complex was synthesized by metalation of pyphos with [Rh(COD)Cl](2) followed by anion exchange with NH(4)PF(6) in excellent yield, and the target rhodium complex was characterized by single-crystal X-ray crystallography. The chiral cationic rhodium complex was utilized in the enantioselective hydroboration of vinylarenes. Excellent regioselectivity and good enantioselectivity were observed, and the ee values were found to be dependent on the electronic properties of para-substituted styrenes.
authors.affiliation: Department of Chemistry, Open Laboratory of Chirotechnology of the Institute of Molecular Technology for Drug Discovery and Synthesis, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong.
authors.forename: Fuk Yee
authors.initials: FY
authors.lastname: Kwong
authors.forename: Qingchuan
authors.initials: Q
authors.lastname: Yang
authors.forename: Thomas C W
authors.initials: TC
authors.lastname: Mak
authors.forename: Albert S C
authors.initials: AS
authors.lastname: Chan
authors.forename: Kin Shing
authors.initials: KS
authors.lastname: Chan