文献类型：期刊文献

英文题名：Cobalt-Catalyzed Asymmetric Aza-Nozaki-Hiyama-Kishi (NHK) Reaction of α-Imino Esters with Alkenyl Halides

作者：Xia, Tingting[1,2];Wu, Yinhui[1,2];Hu, Jiangtao[1,2];Wu, Xianqing[1,2];Qu, Jingping[1,2];Chen, Yifeng[1,2,3]

机构：[1]East China Univ Sci & Technol, Key Lab Adv Mat, Feringa Nobel Prize Scientist Joint Res Ctr, Frontiers Sci Ctr Materiobiol & Dynam Chem,Sch Che, 130 Meilong Rd, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Joint Int Res Lab Precis Chem & Mol Engn, Feringa Nobel Prize Scientist Joint Res Ctr, Frontiers Sci Ctr Materiobiol & Dynam Chem,Sch Che, 130 Meilong Rd, Shanghai 200237, Peoples R China;[3]Chinese Acad Sci, Shanghai Inst Organ Chem, State Key Lab Organometall Chem, Shanghai 200032, Peoples R China

年份：2024

卷号：63

期号：7

外文期刊名：ANGEWANDTE CHEMIE-INTERNATIONAL EDITION

收录：;EI(收录号：20240315383342);WOS:【SCI-EXPANDED(收录号:WOS:001140909700001)，CCR-EXPANDED(收录号:WOS:001140909700001)】；

基金：This work was supported by the National Natural Science Foun-dation of China (22171079, 22371071, 92356301), Natural Science Foundation of Shanghai (21ZR1480400), Shanghai Municipal Science and Technology Major Project (Grant No.2018SHZDZX03), the Program of Introducing Talents of Discipline to Universities (B16017), the China Postdoctoral Science Foundation (2021M701197, 2023T160215), Shanghai Sailing Program (23YF1408800) and the Fundamental Research Funds for the Central Universities. The authors thank the Analysis and Testing Center of East China University of Science and Technology for help with NMR and HRMS analysis.

语种：英文

外文关键词：Alkenyl Halide; Amino Acid Derivatives; Asymmetric Catalysis; Cobalt; NHK Reaction

摘要：Chromium-catalyzed enantioselective Nozaki-Hiyama-Kishi (NHK) reaction represents one of the most powerful approaches for the formation of chiral carbon-heteroatom bond. However, the construction of sterically encumbered tetrasubstituted stereocenter through NHK reaction still posts a significant challenge. Herein, we disclose a cobalt-catalyzed aza-NHK reaction of ketimine with alkenyl halide to provide a convenient synthetic approach for the manufacture of enantioenriched tetrasubstituted alpha-vinylic amino acid. This protocol exhibits excellent functional group tolerance with excellent 99 % ee in most cases. Additionally, this asymmetric reductive method is also applicable to the aldimine to access the trisubstituted stereogenic centers. The cobalt-catalyzed aza-NHK (Nozaki-Hiyama-Kishi) reaction of ketimine has been realized to access diverse alpha-tertiary vinylic amino esters with excellent enantioselectivity and broad functional group tolerance. Notably, both configuration of alkenyl halide provides the same stereochemical outcome of chiral alpha-alkenyl quaternary amino ester, indicating that isomerization of alkenyl fragment might be involved in the catalytic cycle.image