Journal of the American Chemical Society
Journal of the American Chemical Society
5 years ago

A Biphilic Phosphetane Catalyzes N–N Bond-Forming Cadogan Heterocyclization via PIII/PVO Redox Cycling

A Biphilic Phosphetane Catalyzes N–N Bond-Forming Cadogan Heterocyclization via PIII/PVO Redox Cycling
Trevor V. Nykaza, Tyler S. Harrison, Avipsa Ghosh, Rachel A. Putnik, Alexander T. Radosevich
A small-ring phosphacycle, 1,2,2,3,4,4-hexamethylphosphetane, is found to catalyze deoxygenative N–N bond-forming Cadogan heterocyclization of o-nitrobenzaldimines, o-nitroazobenzenes, and related substrates in the presence of hydrosilane terminal reductant. The reaction provides a chemoselective catalytic synthesis of 2H-indazoles, 2H-benzotriazoles, and related fused heterocyclic systems with good functional group compatibility. On the basis of both stoichiometric and catalytic mechanistic experiments, the reaction is proposed to proceed via catalytic PIII/PV═O cycling, where DFT modeling suggests a turnover-limiting (3+1) cheletropic addition between the phosphetane catalyst and nitroarene substrate. Strain/distortion analysis of the (3+1) transition structure highlights the controlling role of frontier orbital effects underpinning the catalytic performance of the phosphetane.

Publisher URL: http://dx.doi.org/10.1021/jacs.7b03260

DOI: 10.1021/jacs.7b03260

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