Wang Fei, Nishimoto Yoshihiro, Yasuda Makoto
Department of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka, 565-0871, Japan.
Innovative Catalysis Science Division, Institute for Open and Transdisciplinary Research Initiatives (ICS-OTRI), Osaka University, Suita, Osaka, 565-0871, Japan.
Angew Chem Int Ed Engl. 2022 Jul 18;61(29):e202204462. doi: 10.1002/anie.202204462. Epub 2022 May 20.
We report a formal carbon-carbon (C-C) bond insertion via the reaction of secondary benzylic halides (fluorides, chlorides, and bromides) with α-diazo esters catalyzed by Lewis acid catalysts. Secondary benzylic halides underwent elongation to afford α,β-diaryl-β-haloesters diastereoselectively. Density functional theory calculation revealed that the present formal C-C bond insertion was the result of Lewis acid-promoted cleavage and the re-formation of a carbon-halogen bond and that the aryl-migration step determined the diastereoselectivity. Various diarylmethyl halides and α-diazo esters were applicable to this reaction system. In addition, ring expansion in cyclic benzylic chlorides was accomplished.
我们报道了在路易斯酸催化剂作用下，仲苄基卤化物（氟化物、氯化物和溴化物）与α-重氮酯反应实现的正式碳-碳（C-C）键插入反应。仲苄基卤化物发生链增长，非对映选择性地生成α,β-二芳基-β-卤代酯。密度泛函理论计算表明，目前的正式C-C键插入反应是路易斯酸促进的碳-卤键断裂和重新形成的结果，且芳基迁移步骤决定了非对映选择性。各种二芳基甲基卤化物和α-重氮酯均可应用于该反应体系。此外，还实现了环状苄基氯化物的扩环反应。
