AcOLeDMAP and BnOLeDMAP: Conformationally Restricted Nucleophilic Catalysts for Enantioselective Rearrangement of Indolyl Acetates and Carbonates

被引：120

作者：

Duffey, Trisha A. ^{[1
]}

Shaw, Scott A. ^{[1
]}

Vedejs, Edwin ^{[1
]}

机构：

[1] Univ Michigan, Dept Chem, Ann Arbor, MI 48109 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2009年 / 131卷 / 01期

基金：

美国国家卫生研究院;

关键词：

INTRAMOLECULAR HECK REACTIONS; ASYMMETRIC-SYNTHESIS; QUATERNARY CARBON; ALPHA-ARYLATION; OXINDOLES; ALLYLATION; LIGANDS;

D O I：

10.1021/ja805541u

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The rate of indotyl O- to C-acetyl or carboxyl rearrangement is accelerated by the electron-withdrawing N-diphenylacetyl group (DPA) using the conformationally restricted chiral catalysts AcOLeDMAP (12b) and BnOLeDMAP (13b). Highly enantioselective conversion to quaternary C-acetylated and C-carboxylated oxindoles is observed, even for substrates containing branched substituents. The rearrangement of the carboxylate substrates 19 occurs with complementary enantiofacial selectivity using catalyst 13b compared to the acetyl migrations of 16 catalyzed by 12b. Access to N-unsubstituted oxindoles is demonstrated by DPA cleavage with Et2NH.

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页码：14 / +

页数：3

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