期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 59, 期 46, 页码 20682-20690出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202008806
关键词
amination; late-stage functionalization; photochemistry; radical anions; tethering
资金
- National Natural Science Foundation of China [21871067]
- Natural Science Foundation of Guangdong Province [2018A030313038]
- Shenzhen Fundamental Research Projects [JCYJ20180306171838187]
- Open Project Program of Beijing National Laboratory for Molecular Sciences [BNLMS201819]
- Harbin Institute of Technology (Shenzhen) (Talent Development Starting Fund from Shenzhen Government)
The utilization of N-centered radicals to synthesize nitrogen-containing compounds has attracted considerable attention recently, due to their powerful reactivities and the concomitant construction of C-N bonds. However, the generation and control of N-centered radicals remain particularly challenging. We report a tethering strategy using SOMO-HOMO-converted distonic radical anions for the site-specific aminations of imidates and amidines with aid of the non-covalent interaction. This reaction features a remarkably broad substrate scope and also enables the late-stage functionalization of bioactive molecules. Furthermore, the reaction mechanism is thoroughly investigated through kinetic studies, Raman spectroscopy, electron paramagnetic resonance spectroscopy, and density functional theory calculations, revealing that the aminations likely involve direct homolytic cleavage of N-H bonds and subsequently controllable 1,5 or 1,6 hydrogen atom transfer.
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