Evaluation of Phosphinoamidoester-Derived Pd Catalysts in the Asymmetric Allylic Alkylation Reaction: Theoretical Studies and Mechanistic Insights

被引：7

作者：

Marinho, Vanda R. D. ^{[1
,2
]}

Prates Ramalho, J. P. ^{[1
,2
]}

Rodrigues, Ana Isabel ^{[3
]}

Burke, Anthony J. ^{[1
,2
]}

机构：

[1] Univ Evora, Dept Quim, P-7000 Evora, Portugal

[2] Univ Evora, Ctr Quim Evora, P-7000 Evora, Portugal

[3] Lab Nacl Energia & Geol, P-1649038 Lisbon, Portugal

来源：

CHIRALITY | 2011年 / 23卷 / 05期

关键词：

asymmetric alkylation; enantioselectivity; P; O-ligands; semiempirical studies; CHIRAL P; O-LIGANDS; X-RAY; LIGANDS; COMPLEXES; COORDINATION; SUBSTITUTION; DENSITY; NMR;

D O I：

10.1002/chir.20936

中图分类号：

R914 [药物化学];

学科分类号：

100701 ;

摘要：

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) = 5 H, R(2) = 5 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. Chirality 23:383-388, 2011. (c) 2011 Wiley-Liss, Inc.

引用

页码：383 / 388

页数：6

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