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Cobalt-catalyzed atroposelective C-H activation/annulation to access N-N axially chiral frameworks.

Tong LiLinlin ShiXinhai WangChen YangDandan YangMao-Ping SongJun-Long Niu
Published in: Nature communications (2023)
The N-N atropisomer, as an important and intriguing chiral system, was widely present in natural products, pharmaceutical lead compounds, and advanced material skeletons. The anisotropic structural characteristics caused by its special axial rotation have always been one of the challenges that chemists strive to overcome. Herein, we report an efficient method for the enantioselective synthesis of N-N axially chiral frameworks via a cobalt-catalyzed atroposelective C-H activation/annulation process. The reaction proceeds under mild conditions by using Co(OAc) 2 ·4H 2 O as the catalyst with a chiral salicyl-oxazoline (Salox) ligand and O 2 as an oxidant, affording a variety of N-N axially chiral products with high yields and enantioselectivities. This protocol provides an efficient approach for the facile construction of N-N atropisomers and further expands the range of of N-N axially chiral derivatives. Additionally, under the conditions of electrocatalysis, the desired N-N axially chiral products were also successfully achieved with good to excellent efficiencies and enantioselectivities.
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