| Abstract
| - A new optically active and large dihedral angle atropisomeric P,N ligand, pyphos, which containsa tertiary phosphine and pyridine moiety, was prepared and resolved through diastereomericcomplexation with chiral palladium amine complexes. The hexafluorophosphate salt of thediastereomers were found to be separable by fractional recyrstallization, while the correspondingchloride salt did not. [Rh(COD)pyphos]PF6 complex was synthesized by metalation of pyphos with[Rh(COD)Cl]2 followed by anion exchange with NH4PF6 in excellent yield, and the target rhodiumcomplex was characterized by single-crystal X-ray crystallography. The chiral cationic rhodiumcomplex was utilized in the enantioselective hydroboration of vinylarenes. Excellent regioselectivityand good enantioselectivity were observed, and the ee values were found to be dependent on theelectronic properties of para-substituted styrenes.
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