A gold(I)‐catalyzed enantioselective dearomatization is achieved via metal‐chiral ligand cooperation. A new and divergent synthesis of chiral bifunctional binaphthyl‐2‐ylphosphines is developed to allow rapid access to these ligands, which in turn facilitate the application of this chemistry to a broad substrate scope including 1‐naphthols, 2‐naphthols, and phenols. Enantiomeric excesses up to 98 % are achieved via selective acceleration of one enantiomer formation enabled by hydrogen bonding between substrate and ligand remote basic group. DFT calculations lend support to the cooperative catalysis and substantiate the reaction stereochemical outcomes.

Efficient access to chiral cyclopentadienyl esters from readily accessible chiral enynyl ester substrates is developed. Typically high levels of chirality transfer realized in this homogeneous gold catalysis are attributed to the intermediacy of a chiral bent allene gold complex. Cyclopentadienyl esters can be prepared in good yields and with excellent enantiomeric excesses. The synthetic utilities of the chiral cyclopentadienyl esters are demonstrated by the Diels− Alder reactions, fluorination, alkylation, and epoxidation without any notable erosion of enantiopurity.

A novel and highly-efficient N-Heterocycle assembly methodology has been established catalyzed by a cobalt-N,N-bidentate complex. The cobalt complex is unprecedented, phosphine-free and easily-prepared, which is demonstrated in the synthesis of...

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.