Morpholine Ketene Aminal as Amide Enolate Surrogate in Iridium-Catalyzed Asymmetric Allylic Alkylation

被引：26

作者：

Sempere, Yeshua ^{[1
]}

Alfke, Jan L. ^{[1
]}

Rossler, Simon L. ^{[1
]}

Carreira, Erick M. ^{[1
]}

机构：

[1] Eidgenoss Tech Hsch Zurich, Organ Chem Lab, HCI H335,Vladimir Prelog Weg 3, CH-8093 Zurich, Switzerland

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2019年 / 58卷 / 28期

基金：

瑞士国家科学基金会;

关键词：

alkylation; allylation; amides; enantioselectivity; iridium; 2,4-DISUBSTITUTED CYCLOPENTENONES; ENANTIOSELECTIVE SYNTHESIS; ALLYLATION; REARRANGEMENT; ACIDITIES; ACETATES;

D O I：

10.1002/anie.201903090

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Morpholine ketene aminal is employed in iridium-catalyzed asymmetric allylic alkylation reactions as a surrogate for amide enolates to prepare gamma,delta-unsaturated beta-substituted morpholine amides. Kinetic resolution or, alternatively, stereospecific substitution affords the corresponding products in high enantiomeric excess. The utility of the products generated by this method has been showcased by their further elaboration into amines, ketones, or acyl silanes. A putative catalytic intermediate (eta(3)-allyl)iridium(III) with achiral P,Olefin-ligand was synthetized and characterized for the first time.

引用

页码：9537 / 9541

页数：5

共 51 条

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