Thorat Vijaykumar H, Hsieh Jen-Chieh, Cheng Chien-Hong
Department of Chemistry, Tamkang University, New Taipei City 25137, Taiwan (R.O.C.).
Department of Chemistry, National Tsing Hua University, Hsinchu 30013, Taiwan (R.O.C.).
Org Lett. 2020 Aug 21;22(16):6623-6627. doi: 10.1021/acs.orglett.0c02393. Epub 2020 Aug 12.
A novel procedure for the transition-metal-free tandem cyclization/-arylation reaction sequence of an aryne with a 1,2,3,4-benzothiatriazine-1,1-dioxide is reported. This reaction goes through the intramolecular homolytic cyclization to generate an N-H biaryl sultam intermediate, which enables aryne insertion to access diversely functionalized biaryl sultam derivatives with high yields. The mechanism study indicates that homolytic cyclization is executed by a diradical species, initiated from the thermal decomposition of 1,2,3,4-benzothiatriazine-1,1-dioxide to release a nitrogen molecule.
报道了一种新颖的无过渡金属的芳炔与1,2,3,4-苯并噻二嗪-1,1-二氧化物的串联环化/芳基化反应序列。该反应通过分子内均裂环化生成N-H联芳基磺胺中间体，这使得芳炔插入能够以高收率获得各种功能化的联芳基磺胺衍生物。机理研究表明，均裂环化由双自由基物种进行，该双自由基物种由1,2,3,4-苯并噻二嗪-1,1-二氧化物的热分解引发以释放一个氮分子。
