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

被引：43
|
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
收藏
页码：2873 / 2878
页数：6
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