期刊
NATURE CHEMISTRY
卷 7, 期 12, 页码 987-994出版社
NATURE PUBLISHING GROUP
DOI: 10.1038/NCHEM.2366
关键词
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资金
- NIH/NIGMS [GM112492]
- Bristol-Myers-Squibb with 'Freedom to Discover' grant
C-H bond oxidation reactions underscore the existing paradigm wherein high reactivity and high selectivity are inversely correlated. The development of catalysts capable of oxidizing strong aliphatic C(sp(3))-H bonds while displaying chemoselectivity (that is, tolerance of more oxidizable functionality) remains an unsolved problem. Here, we describe a catalyst, manganese tert-butylphthalocyanine [Mn((BuPc)-Bu-t)], that is an outlier to the reactivity-selectivity paradigm. It is unique in its capacity to functionalize all types of C(sp(3))-H bond intramolecularly, while displaying excellent chemoselectivity in the presence of pi functionality. Mechanistic studies indicate that [Mn((BuPc)-Bu-t)] transfers bound nitrenes to C(sp(3))-H bonds via a pathway that lies between concerted C-H insertion, observed with reactive noble metals such as rhodium, and stepwise radical C-H abstraction/rebound, as observed with chemoselective base metals such as iron. Rather than achieving a blending of effects, [Mn((BuPc)-Bu-t)] aminates even 1 degrees aliphatic and propargylic C-H bonds, demonstrating reactivity and selectivity unusual for previously known catalysts.
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