Preparation and catalytic properties of palladium(0) and rhodium(I) complexes containing new chiral P,N-ligands derived from carbohydrates

New chiral P,N-chelates o-Ph2PC6H4CHNR (R=carbohydrate residue) derived from d -glucose and d -mannose were described. The synthesis of palladium(0) and rhodium(I) complexes of respective formula [Pd(P,N-chelate)(fumarodinitrile)] and [Rh(1,5-cyclooctadiene)(P,N-chelate)]BF4 was performed. It was found that the ligands effectively discriminate between the enantioface of fumarodinitrile in the Pd(0) species, prompting up to 100% diastereomeric excess when R is a 2,3,4-tri-O-acetylated glucoside moiety linked to N through C6. The catalytic activity of the complexes towards allylic alkylation and olefin hydroboration was also examined.