A Chiral Bis(arsine) Ligand: synthesis and applications in Palladium catalyzed asymmetric Allylic Alkylations

Article

Authorship

UBERMAN, PAULA MARINA ; Caira, Mino R. ; MARTIN, SANDRA ELIZABETH

Date

2013

Publishing House and Editing Place

American Chemical Society

Magazine

ORGANOMETALLICS, vol. 32 (pp. 3220-3226) American Chemical Society

Summary Information provided by the agent in SIGEVA

The new chiral bis(arsine) ligand N,N?-bis[2?- (diphenylarsino)benzoyl]-(1R,2R)-cyclohexanediamine (BiAsBA, 3), based on the backbone of the Trost modular ligand (TML), was synthesized in three steps. A useful approach to introduce the ?AsPh2 group on arsine ligands by Pd-catalyzed arsination was used. The molecular structure and configuration of the BiAsBA ligand was determined by single-crystal X-ray crystallography. In the asymmetric allylic alkylation of 1,3-diphenyl-2- propenyl acetate wit... The new chiral bis(arsine) ligand N,N?-bis[2?- (diphenylarsino)benzoyl]-(1R,2R)-cyclohexanediamine (BiAsBA, 3), based on the backbone of the Trost modular ligand (TML), was synthesized in three steps. A useful approach to introduce the ?AsPh2 group on arsine ligands by Pd-catalyzed arsination was used. The molecular structure and configuration of the BiAsBA ligand was determined by single-crystal X-ray crystallography. In the asymmetric allylic alkylation of 1,3-diphenyl-2- propenyl acetate with dimethyl malonate very high to complete conversion and modest enantioselectivity were achieved. Despite the low enantioselectivity obtained, the bis(arsine) ligand BiAsBA showed significant potential, since it provided a higher ee value than the phosphorus-containing homologous “Trost standard ligand” (TSL) with the same substrate.