Intramolecular hydride transfer onto arynes: redox-neutral and transition metal-free C(sp3)-H functionalization of amines

被引：45

作者：

Idiris, Fahima I. M. ^{[1
]}

Majeste, Cecile E. ^{[1
]}

Craven, Gregory B. ^{[1
]}

Jones, Christopher R. ^{[1
]}

机构：

[1] Queen Mary Univ London, Sch Biol & Chem Sci, Mile End Rd, London E1 4NS, England

来源：

CHEMICAL SCIENCE | 2018年 / 9卷 / 11期

基金：

英国工程与自然科学研究理事会;

关键词：

C-H FUNCTIONALIZATION; DIELS-ALDER REACTION; BOND FUNCTIONALIZATION; CYCLIC AMINES; ASYMMETRIC-SYNTHESIS; COUPLING REACTIONS; C-SP3-H BONDS; BENZYNE; CHEMISTRY; ACTIVATION;

D O I：

10.1039/c8sc00181b

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Transition metal-free intramolecular hydride transfer onto arynes is reported for the first time. This unique transformation is utilized in redox-neutral intermolecular alpha-functionalization reactions of different tertiary amines, generating C(sp(3))-C(sp(3)/sp(2)/sp) bonds in a single synthetic operation. Deuterium labeling studies support initial cleavage of the alpha-C-H bond via intramolecular 1,5-hydride transfer onto the aryne, which leads to activation of a range of integrated pronucleophiles and ultimately affords a new approach to cross-dehydrogenative coupling reactions which utilize aryne intermediates.

引用

页码：2873 / 2878

页数：6

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