Application of SDP Ligands for Pd-catalyzed allylic alkylation

作者：Xie JH^*; Duan HF; Fan BM; Cheng X; Wang LX; Zhou QL

来源：Advanced Synthesis & Catalysis, 2004, 346(6): 625-632.

DOI：10.1002/adsc.200404003

• allylic alkylation
• asymmetric catalysis
• diphosphine ligands
• palladium
• spirobiindane

Chiral spiro diphosphines (SDP) are efficient ligands for the Pd-catalyzed asymmetric allylic alkylation of 1,3-diphenyl-2-propenyl acetate with dimethyl malonate and related nucleophiles. The newly synthesized ligand DMM-SDP (1e) with 3,5-dimethyl-4-methoxy groups on the P-phenyl rings of the phosphine shows the highest enantioselectivity (up to 99.1% ee). Diethylzinc as a base is critical for obtaining high enantioselectivity in the allylic alkylation using beta-dicarbonyl nucleophiles. The structure of catalyst [PdCl(2)((S)-SDP)] was determined by single crystal X-ray diffraction. The SDP ligands create an effective asymmetric environment around the palladium, resulting in high enantioselectivities for the asymmetric allylic alkylation reaction.

• 出版日期2004-5
• 单位南开大学