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

You might also like
Discover & Discuss Important Research

Keeping up-to-date with research can feel impossible, with papers being published faster than you'll ever be able to read them. That's where Researcher comes in: we're simplifying discovery and making important discussions happen. With over 19,000 sources, including peer-reviewed journals, preprints, blogs, universities, podcasts and Live events across 10 research areas, you'll never miss what's important to you. It's like social media, but better. Oh, and we should mention - it's free.

  • Download from Google Play
  • Download from App Store
  • Download from AppInChina

Researcher displays publicly available abstracts and doesn’t host any full article content. If the content is open access, we will direct clicks from the abstracts to the publisher website and display the PDF copy on our platform. Clicks to view the full text will be directed to the publisher website, where only users with subscriptions or access through their institution are able to view the full article.