Medium-Ring Nitrogen Heterocycles through Migratory Ring Expansion of Metalated Ureas

被引：102

作者：

Hall, Jessica E. ^{[1
]}

Matlock, Johnathan V. ^{[1
]}

Ward, John W. ^{[1
]}

Gray, Katharine V. ^{[2
]}

Clayden, Jonathan ^{[1
]}

机构：

[1] Univ Bristol, Sch Chem, Cantocks Close, Bristol BS8 1TS, Avon, England

[2] Univ Manchester, Sch Chem, Oxford Rd, Manchester M13 9PL, Lancs, England

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2016年 / 55卷 / 37期

基金：

英国工程与自然科学研究理事会;

关键词：

heterocycles; indolines; organolithium; ring expansion; tetrahydroquinolines; AMINO-ACID-DERIVATIVES; ONE-POT SYNTHESIS; ORIENTED SYNTHESIS; LITHIATED UREAS; ALPHA-ARYLATION; ARYL MIGRATION; REARRANGEMENT; CYCLIZATION; LACTAMS; ATROPISOMERISM;

D O I：

10.1002/anie.201605714

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Simple benzo-fused nitrogen heterocycles (indolines, tetrahydroquinolines, and their homologues) undergo migratory ring expansion through deprotonation of their benzylic urea derivatives with lithium diisopropylamide (LDA) in the presence of N,N-dimethylpropylideneurea (DMPU). The products of the reactions are benzodiazepines, benzodiazocines, and their homologues, with ring sizes of 8-12. The reactions tolerate a range of substituent patterns and types, and may exhibit enantiospecificity or diastereoselectivity. Considerable complexity is rapidly generated in an efficient synthesis of these otherwise difficult-to-obtain medium-ring nitrogen heterocycles.

引用

页码：11153 / 11157

页数：5

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