文献类型：期刊文献

英文题名：Regio- and Enantioselective γ-Allylic Alkylation of In Situ-Generated Free Dienolates via Scandium/Iridium Dual Catalysis

作者：Zhang, Jian[1,2];Yang, Wu-Lin[1,2];Zheng, Hanliang[3];Wang, Yi[1,2];Deng, Wei-Ping[1,2,3]

机构：[1]East China Univ Sci & Technol, Shanghai Key Lab Chem Biol, 130 Meilong Rd, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Sch Pharm, 130 Meilong Rd, Shanghai 200237, Peoples R China;[3]Zhejiang Normal Univ, Dept Chem, Key Lab, Minist Educ Adv Catalysis Mat, Jinhua 321004, Zhejiang, Peoples R China

年份：2022

卷号：61

期号：19

外文期刊名：ANGEWANDTE CHEMIE-INTERNATIONAL EDITION

收录：;EI(收录号：20221111776251);WOS:【SCI-EXPANDED(收录号:WOS:000767061400001)，CCR-EXPANDED(收录号:WOS:000767061400001)】；

基金：This work is supported by the National Natural Science Foundation of China (nos. 21901072, 21971062, 22171082, and 22171081) and the Shanghai Frontiers Science Center of Optogenetic Techniques for Cell Metabolism. We thank the Research Center of Analysis and Test of the East China University of Science and Technology for the assistance with the HRMS and NMR analyses.

语种：英文

外文关键词：Dual Catalysis; Allylation; Asymmetric Synthesis; Dienolates; Iridium

摘要：An unprecedented asymmetric gamma-allylic alkylation of free dienolates via Sc/Ir dual catalysis is reported, which affords a range of synthetically versatile gamma-allylic crotonaldehydes in high efficiency with excellent chemo-, regio-, and enantioselectivities. The dienolates bearing no essential auxiliary groups were generated in situ by scandium triflate-mediated Meinwald rearrangement of vinyloxiranes atom-economically. With the assistance of computational density functional theory calculations, a Sc/Ir bimetallic catalytic cycle was proposed to illustrate the reaction mechanism.