149742-71-2Relevant articles and documents
A Biphilic Phosphetane Catalyzes N-N Bond-Forming Cadogan Heterocyclization via PIII/PV = O Redox Cycling
Nykaza, Trevor V.,Harrison, Tyler S.,Ghosh, Avipsa,Putnik, Rachel A.,Radosevich, Alexander T.
supporting information, p. 6839 - 6842 (2017/05/29)
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.
