Rhodium-Catalyzed Sequential Allylic Amination and Olefin Hydroacylation Reactions: Enantioselective Synthesis of Seven-Membered Nitrogen Heterocycles

被引：75

作者：

Arnold, Jeffrey S. ^{[1
]}

Mwenda, Edward T. ^{[1
]}

Nguyen, Hien M. ^{[1
]}

机构：

[1] Univ Iowa, Dept Chem, Iowa City, IA 52242 USA

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2014年 / 53卷 / 14期

关键词：

allylic amination; asymmetric catalysis; intramolecular hydroacylation; nitrogen heterocycles; rhodium; KINETIC ASYMMETRIC TRANSFORMATIONS; INTRAMOLECULAR HYDROACYLATION; COOPERATIVE CATALYSIS; C-H; AMINES; ALCOHOLS; CYCLIZATION; HYDROAMINATION; SUBSTITUTION; NUCLEOPHILES;

D O I：

10.1002/anie.201310354

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Dynamic kinetic asymmetric amination of branched allylic acetimidates has been applied to the synthesis of 2-alkyl-dihydrobenzoazepin-5-ones. These seven-membered-ring aza ketones are prepared in good yield with high enantiomeric excess by rhodium-catalyzed allylic substitution with 2-amino aryl aldehydes followed by intramolecular olefin hydroacylation of the resulting alkenals. This two-step procedure is amenable to varied functionality and proves useful for the enantioselective preparation of these ring systems.

引用

页码：3688 / 3692

页数：5

共 59 条

[1]

[Anonymous], ANGEW CHEM

[2]

Arnold J. S., 2013, SYNTHESIS-STUTTGART, P2101

[3] Rhodium-catalyzed regio- and enantioselective amination of racemic secondary allylic trichloroacetimidates with N-methyl anilines [J].