A new chiral P,N-ligand derived from 1-phenylphospholane-2-carboxylic acid (phenyl-P-proline) for palladium-catalyzed asymmetric allylic substitution reactions

作者：Sun XM; Koizumi M; Manabe K; Kobayashi S^*

来源：Advanced Synthesis & Catalysis, 2005, 347(15): 1893-1898.

DOI：10.1002/adsc.200505234

• allylic substitution
• asymmetric catalysis
• palladium
• P,N-ligands

New types of P,N-ligands, cis- and trans-3, containing a tetrahydroisoquinoline skeleton as an N-donor were synthesized from (1R,2S)-1-phenylphospholane-2-carboxylic acid (phenyl-P-proline, 1). The cis isomer, cis-3, was found to act as an excellent ligand in palladium-catalyzed asymmetric allylic substitution reactions. The reactions of 1,3-diphenyl-2-propenyl acetate (5) with several nucleophiles in the presence of [Pd(pi-allyl)Cl](2), cis-3 (Pd:ligand= 1:2), and a base afforded the desired products in high yields with high enantioselectivity. It was suggested that these ligands did not serve as PN-bidentate ligands but as P-monodentate ligands in these reactions.

• 出版日期2005-12