Zhu Xiaohan, Wu Hongli, Wang Yishou, Huang Genping, Wang Fen, Li Xingwei
School of Chemistry and Chemical Engineering, Shaanxi Normal University Xi'an 710062 China
Department of Chemistry, School of Science and Tianjin Key Laboratory of Molecular Optoelectronic Sciences, Tianjin University Tianjin 300072 China
Chem Sci. 2023 Jul 15;14(32):8564-8569. doi: 10.1039/d3sc02800c. eCollection 2023 Aug 16.
N-N axially chiral biaryls represent a rarely explored class of atropisomeric compounds. We hereby report rhodium-catalyzed enantioselective [4 + 2] oxidative annulation of internal alkynes with benzamides bearing two classes of N-N directing groups. The coupling occurs under mild conditions NH and CH annulation through the dynamic kinetic transformation of the directing group and is highly enantioselective with good functional tolerance. Computational studies of a coupling system at the DFT level has been conducted, and the alkyne insertion was identified as the enantio-determining as well as the turnover-limiting step.
N-N轴手性联芳基代表了一类鲜少被探索的阻转异构化合物。我们在此报告铑催化的带有两类N-N导向基团的苯甲酰胺与内炔的对映选择性[4 + 2]氧化环化反应。该偶联反应在温和条件下通过导向基团的动态动力学转化实现N-H和C-H环化，具有高度的对映选择性和良好的官能团耐受性。已在密度泛函理论（DFT）水平上对一个偶联体系进行了计算研究，并且确定炔烃插入是对映体决定步骤以及周转限制步骤。
