文献类型：期刊文献

英文题名：Nickel-Catalyzed Enantioselective Reductive Alkyl-Carbamoylation of Internal Alkenes

作者：Wu, Xianqing[1];Turlik, Aneta[2];Luan, Baixue[1];He, Feng[1];Qu, Jingping[1];Houk, K. N.[2];Chen, Yifeng[1]

机构：[1]East China Univ Sci & Technol, Key Lab Adv Mat & Joint Int Res Lab Precis Chem &, Feringa Nobel Prize Scientist Joint Res Ctr, Frontiers Sci Ctr Materiobiol & Dynam Chem,Sch Ch, Shanghai 200237, Peoples R China;[2]Univ Calif Los Angeles, Dept Chem & Biochem, 405 Hilgard Ave, Los Angeles, CA 90024 USA

年份：2022

卷号：61

期号：36

外文期刊名：ANGEWANDTE CHEMIE-INTERNATIONAL EDITION

收录：;EI(收录号：20223012412406);WOS:【SCI-EXPANDED(收录号:WOS:000829335600001)，CCR-EXPANDED(收录号:WOS:000829335600001)】；

基金：This work was supported by NSFC/China (22171079), the National Science Foundation (grant CHE-1764328), Natural Science Foundation of Shanghai (21ZR1480400), Shanghai Rising-Star Program (20QA1402300), Shanghai Municipal Science and Technology Major Project (Grant No.2018SHZDZX03), the Program of Introducing Talents of Discipline to Universities (B16017) and the China Postdoctoral Science Foundation (2021M701197). A.T. acknowledges the support of the National Institutes of Health under Ruth L. Kirschstein National Research Service Award F32GM134709. Calculations were performed on the Hoffman2 cluster at the University of California, Los Angeles, and the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by the National Science Foundation (grant OCI-1053575). The authors thank the Analysis and Testing Center of East China University of Science and Technology for help with NMR analysis.

语种：英文

外文关键词：Density Functional Theory; Internal Alkenes; Lactams; Nickel Catalysis; Vicinal Stereogenic Centers

摘要：Herein, we leverage the Ni-catalyzed enantioselective reductive dicarbofunctionalization of internal alkenes with alkyl iodides to enable the synthesis of chiral pyrrolidinones bearing vicinal stereogenic centers. The application of newly developed (1-Nap)Quinim is critical for formation of two contiguous stereocenters in high yield, enantioselectivity, and diastereoselectivity. This catalytic system also improves both the yield and enantioselectivity in the synthesis of alpha,alpha-dialkylated gamma-lactams. Computational studies reveal that the enantiodetermining step proceeds with a carbamoyl-Ni-I intermediate that is reduced by the Mn reductant prior to intramolecular migratory insertion. The presence of the t-butyl group of the Quinim ligand leads to an unfavorable distortion of the substrate in the TS that leads to the minor enantiomer. Calculations also support an improvement in enantioselectivity with (1-Nap)Quinim compared to (p-tol)Quinim.