Journal
NATURE CHEMISTRY
Volume 10, Issue 6, Pages 583-591Publisher
NATURE PUBLISHING GROUP
DOI: 10.1038/s41557-018-0020-0
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Funding
- NIGMS Maximizing Investigators' Research Award MIRA [R35 GM122525]
- NIH [1 F32GM112501-01A1]
- NATIONAL INSTITUTE OF GENERAL MEDICAL SCIENCES [F32GM112501, R35GM122525] Funding Source: NIH RePORTER
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Reactions that directly install nitrogen into C-H bonds of complex molecules are significant because of their potential to change the chemical and biological properties of a given compound. Although selective intramolecular C-H amination reactions are known, achieving high levels of reactivity while maintaining excellent site selectivity and functional-group tolerance remains a challenge for intermolecular C-H amination. Here, we report a manganese perchlorophthalocyanine catalyst [Mn-III(CIPc)] for intermolecular benzylic C-H amination of bioactive molecules and natural products that proceeds with unprecedented levels of reactivity and site selectivity. In the presence of a Bronsted or Lewis acid, the [Mn-III(CIPc)]-catalysed C-H amination demonstrates unique tolerance for tertiary amine, pyridine and benzimidazole functionalities. Mechanistic studies suggest that C-H amination likely proceeds through an electrophilic metallonitrene intermediate via a stepwise pathway where C-H cleavage is the rate-determining step of the reaction. Collectively, these mechanistic features contrast with previous base-metal-catalysed C-H aminations and provide new opportunities for tunable selectivities.
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