Evaluation of phosphinoamidoester-derived Pd catalysts in the asymmetric allylic alkylation reaction: theoretical studies and mechanistic insights |
| |
Authors: | Marinho Vanda R D Ramalho J P Prates Rodrigues Ana Isabel Burke Anthony J |
| |
Affiliation: | 1. Departamento de Química and Centro de Química de évora, Universidade de évora, Rua Rom?o Romalho 59, 7000 évora, Portugal;2. Laboratório Nacional de Energia e Geologia, Estrada do Pa?o do Lumiar, Edifício F, 1649‐038 Lisboa, Portugal |
| |
Abstract: | Two simple hemilabile P,O-coordinating phosphinoamidoester ligands 6a and 6b were synthesized and studied in the Pd(0)-catalyzed asymmetric allylic alkylation of rac-1,3-diphenylpropenyl acetate affording a highest ee of 83% ee with 6a. To gain an insight into the actual mechanism of this catalytic reactions, which had previously been investigated with a first generation family of P,O-coordinating phosphinoamido-alcohol ligands-4a and 4b-a semiempirical computational study was carried out with the Pd-allyl complexes formed from both 4a and 6a including Hitchcock's phosphinoamido-alcohol ligand 5 (R(1)= H, R(2)= Ph). The results of this study substantiate a working model that has previously been proposed for this reaction using hemilabile P,O-coordinating phosphinoamido-type ligands. |
| |
Keywords: | asymmetric alkylation enantioselectivity P,O‐ligands semiempirical studies |
本文献已被 PubMed 等数据库收录! |
|