A Biphilic Phosphetane Catalyzes N–N Bond-Forming Cadogan Heterocyclization via P[superscript III]/P[superscript V]═O Redox Cycling
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Radosevich_A biphilic.pdf
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Author(s)
Putnik, Rachel A.
Nykaza, Trevor Vincent
Harrison, Tyler Steven
Ghosh, Avipsa
Radosevich, Alexander T.
Date Issued
May 2017
Journal
Journal of the American Chemical Society
Publisher
American Chemical Society (ACS)
Citation
Nykaza, Trevor V., et al. “A Biphilic Phosphetane Catalyzes N–N Bond-Forming Cadogan Heterocyclization via P[superscript III]/P[subscript V] ═O Redox Cycling.” Journal of the American Chemical Society, vol. 139, no. 20, May 2017, pp. 6839–42.
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Author's final manuscript
Abstract
A small-ring phosphacycle, 1,2,2,3,4,4-hexamethylphosphetane, is found to catalyze deoxygenative N-N bond-forming Cadogan h eterocyclization 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 P[superscript III]/P[superscript V] = 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.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1021/JACS.7B03260
