Sun Xing-Yun, Song Jia-Yu, Wang Bai-Lin, Zhou Sheng-Suo, Ou Zhi-Xiong, Li Li-Bo, Wang Zheng, Wang Xing-Wang
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, P. R. China.
State Key Laboratory of Organometallic Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, P. R. China.
J Org Chem. 2024 Apr 5;89(7):4904-4915. doi: 10.1021/acs.joc.4c00118. Epub 2024 Mar 18.
The palladium-catalyzed highly regioselective asymmetric allylic alkylation of 3'-indolyl-3-oxindole derivatives with Morita-Baylis-Hillman (MBH) carbonates was developed to facilely construct chiral 3,3'-bisindole derivatives under mild reaction conditions. The regioselectivity (α/γ) of MBH carbonates was efficiently switched in the presence of chiral oxalamide phosphine or spiroketal-based diphosphine/Pd(0) complexes as a chiral catalyst. A series of multifunctional 3,3'-bisindole derivatives with all-carbon quaternary stereogenic centers were obtained in high yields with good to excellent enantio-, diastereo-, and regioselectivity. The present process is endowed with some salient features such as broad substrate scope, -protecting group-free, excellent stereoselectivity, as well as adjustable regioselectivity.
开发了钯催化的3'-吲哚基-3-氧化吲哚衍生物与森田-贝利斯-希尔曼（MBH）碳酸酯的高度区域选择性不对称烯丙基烷基化反应，以便在温和的反应条件下轻松构建手性3,3'-双吲哚衍生物。在手性草酰胺膦或基于螺缩酮的双膦/Pd(0)配合物作为手性催化剂存在下，MBH碳酸酯的区域选择性（α/γ）能有效切换。以良好至优异的对映选择性、非对映选择性和区域选择性，高产率地获得了一系列具有全碳季碳立体中心的多功能3,3'-双吲哚衍生物。本方法具有底物范围广、无需保护基团、优异的立体选择性以及可调节的区域选择性等显著特点。
