Alkene functionalization with a single-atom catalyst (SAC) which merges homogeneous and heterogeneous catalysis is a fascinating route to obtain high-value-added molecules. However, C–N bond formation of alkene with SAC is still unexplored. Herein, a bimetal-organic framework-derived Co–N/C catalyst with an atomically dispersed cobalt center is reported to show good activity of chemoselective aziridination/oxyamination reactions from alkene and hydroxylamine, and late-stage functionalization of complex alkenes and diversified synthetic transformations of the aziridine product further expand the utility of this method. Moreover, this system proceeds without external oxidants and exhibits mild, atom-economic, and recyclable characters. Detailed spectroscopic characterizations and mechanistic studies revealed the structure of the catalytic center and possible intermediates involved in the mechanism cycle.

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This paper is dedicated to the 70th anniversary of Huazhong University of Science and Technology, and to Prof. Matthias Beller on the occasion of his 60th birthday.An easily prepared core-shell heterogeneous nanocobalt catalyst was reported, which could achieve selective reduction of Nheteroarenes with ammonia borane under mild conditions and ambient atmosphere. Various quinoline, quinoxaline, naphthyridine, isoquinoline, acridine, and phenanthroline derivatives were hydrogenated with high selectivity and efficiency. Notably, substrates bearing sensitive functional groups under molecular hydrogen reduction conditions, such as cyano, ester, and halogens were well tolerated by the catalytic system. Moreover, with our novel method several bioactive molecules were prepared. Also, this catalyst could be applied in the liquid organic hydrogen storage system by reversible hydrogenation and dehydrogenation of heteroarene in high efficiencies.

Aziridine synthesis from readily available alkene has been a long-standing point of interest for organic chemists, owing to the widely existence in bioactive compounds and plentiful synthetic derivatizations of aziridines. Compared with using iminoiodinane or azide as the nitrogen source, the seeking for catalytic systems employing novel nitrogen transfer reagent under external oxidant-free conditions are the cutting-edge techniques in this field. Herein, a pioneering nano-cobalt catalyzed chemo-selective aziridination/oxyamination reaction from alkene and hydroxylamine is developed, this system proceeds without external oxidant and exhibits mild, efficient, atom-economic and recyclable characters. Late-stage aziridinations of drug-derived alkenes and diversified synthetic transformation of the aziridine product further expands the utility of this method. Moreover, this novel methodology represents a rare example of alkene difunctionalization under nano-catalyst, which bridges the gap between homo- and heterogeneous catalysis. Moreover, the full characterizations of the nano-cobalt catalyst and mechanistic studies including deuterium-labeled experiment and Hammet analysis were conducted, while a reasonable mechanism was also suggested accordingly.

Aziridine synthesis from readily available alkene has been a long-standing point of interest for organic chemists, owing to their widely existence in bioactive compounds and plentiful synthetic derivatiza-tions. Herein, a nano-cobalt catalyzed chemo-selective aziridina-tion/oxyamination reaction from alkene and hydroxylamine was de-veloped under room temperature, this system proceeds without exter-nal oxidant and exhibits mild, efficient, atom-economic and recyclable characters, which makes this discovery more practical and fascinating. Late-stage aziridinations of drug-derived olefins and diversified syn-thetic transformation of the aziridine product further expanded the utility of this method. Moreover, this novel methodology represents a rare example of alkene difunctionalization under nano-catalyst, which bridges the gap between homo- and heterogeneous catalysis. Finally, mechanistic studies including deuterium-labeled experiment and Hammet analysis were conducted, and a potential mechanism was proposed accordingly.