Triiodide-Mediated δ-Amination of Secondary C-H Bonds

被引：215
作者：
Wappes, Ethan A. [1 ]
Fosu, Stacy C. [1 ]
Chopko, Trevor C. [1 ]
Nagib, David A. [1 ]
机构：
[1] Ohio State Univ, Dept Chem & Biochem, Columbus, OH 43210 USA
来源：
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2016年 / 55卷 / 34期
基金：
美国国家卫生研究院;
关键词：
amination; C-H functionalization; radical chemistry; hydrogen atom transfer; triiodide; CATALYZED INTRAMOLECULAR AMINATION; HETEROCYCLE SYNTHESIS; RADICAL CATIONS; FUNCTIONALIZATION; C(SP(3))-H; ACTIVATION; GENERATION; AMINES; HYDROAMINATION; CONSTRUCTION;
D O I：
10.1002/anie.201604704
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
The C-delta-H amination of unactivated, secondary C-H bonds to form a broad range of functionalized pyrrolidines has been developed by a triiodide (I-3(-))-mediated strategy. By in situ 1) oxidation of sodium iodide and 2) sequestration of the transiently generated iodine (I-2) as I-3(-), this approach precludes undesired I-2-mediated decomposition which can otherwise limit synthetic utility to only weak C(sp(3)) H bonds. The mechanism of this triiodide-mediated cyclization of unbiased, secondary C(sp(3))-H bonds, by either thermal or photolytic initiation, is supported by NMR and UV/Vis data, as well as intercepted intermediates.
引用
收藏
页码：9974 / 9978
页数：5
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