Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, No. 2318, Yuhangtang Road, Hangzhou, 311121, P. R. China.
Suzhou Research Institute and State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, P. R. China.
Angew Chem Int Ed Engl. 2019 Jan 14;58(3):897-901. doi: 10.1002/anie.201813071. Epub 2018 Dec 7.
A palladium-catalyzed enantioselective sequential ring-opening/cross-coupling of cyclobutanones is disclosed that provides chiral indanones bearing C3-quaternary stereocenters. The reaction process involves palladium-catalyzed nucleophilic addition of cyclobutanones and aryl halides, enantioselective β-carbon elimination, and intermolecular trapping of a transient σ-alkylpalladium complex with boronic acids. Alternatively, an intramolecular cyclopropanation is realized through C-H bond functionalization in the absence of external coupling reagents, affording chiral cyclopropane-fused-indanones in good yields and enantioselectivity.
公开了一种钯催化的环丁酮的对映选择性串联开环/交叉偶联反应，该反应提供了具有 C3-季碳立体中心的手性茚满酮。该反应过程涉及钯催化的环丁酮和芳基卤化物的亲核加成、β-碳对映选择性消除以及硼酸与瞬态σ-烷基钯络合物的分子间捕获。或者，在没有外部偶联试剂的情况下，通过 C-H 键官能化实现分子内环丙基化，以良好的收率和对映选择性得到手性环丙基稠合茚满酮。
