Ge Jiemin, Wu Xueli, Bao Xiaoguang
College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China.
Chem Commun (Camb). 2019 May 28;55(43):6090-6093. doi: 10.1039/c9cc02294e. Epub 2019 May 9.
The Rh(ii)-catalyzed annulation of N-sulfonyl-1,2,3-triazoles with 1,3,5-triazinanes leading to the octahydro-1H-purine derivatives with moderate to good yields is described in this communication. Mechanistic studies via DFT calculations suggest that the 1,3,5-triazinanes might undergo a formal [6+3] cycloaddition with the Rh(ii)-azavinyl carbene intermediates, which are generated from Rh(ii)-catalyzed denitrogenation of 1,2,3-triazoles. Afterwards, ring-closure of the formed nine-membered ring intermediate via intramolecular nucleophilic addition followed by subsequent rearrangements could afford the final octahydro-1H-purine derivatives.
本文报道了铑（II）催化N-磺酰基-1,2,3-三唑与1,3,5-三嗪烷的环化反应，以中等至良好的产率生成八氢-1H-嘌呤衍生物。通过密度泛函理论（DFT）计算进行的机理研究表明，1,3,5-三嗪烷可能与铑（II）-氮杂乙烯基卡宾中间体发生形式上的[6+3]环加成反应，该中间体由铑（II）催化的1,2,3-三唑脱氮反应生成。之后，通过分子内亲核加成使形成的九元环中间体闭环，随后进行重排，可得到最终的八氢-1H-嘌呤衍生物。
