文献类型：期刊文献

英文题名：Palladium-Catalyzed Enantioselective Multicomponent Cross-Coupling of Trisubstituted Olefins

作者：Huang, Wenyi[1,2];Xi, Yang[1,2];Pan, Deng[3];Fan, Linlin[1,2];Fang, Ke[1,2];Huang, Genping[3];Zhu, Wei-Hong[1,2];Qu, Jingping[1,2];Chen, Yifeng[1,2,4,5]

机构：[1]East China Univ Sci & Technol, Feringa Nobel Prize Scientist Joint Res Ctr, Frontiers Sci Ctr Materiobiol & Dynam Chem, Sch Chem & Mol Engn,Key Lab Adv Mat, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Feringa Nobel Prize Scientist Joint Res Ctr, Frontiers Sci Ctr Materiobiol & Dynam Chem, Sch Chem & Mol Engn,Joint Int Res Lab Precis Chem, Shanghai 200237, Peoples R China;[3]Tianjin Univ, Sch Sci, Dept Chem, Tianjin 300072, Peoples R China;[4]Chinese Acad Sci, Shanghai Inst Organ Chem, State Key Lab Organometall Chem, Shanghai 200032, Peoples R China;[5]Henan Normal Univ, Sch Chem & Chem Engn, Xinxiang 453007, Peoples R China

年份：2024

卷号：146

期号：24

起止页码：16892

外文期刊名：JOURNAL OF THE AMERICAN CHEMICAL SOCIETY

收录：;EI(收录号：20242416258744);WOS:【SCI-EXPANDED(收录号:WOS:001242817900001)】；

基金：This work was supported by the National Natural Science Foundation of China (22171079, 22371071, 22073066, 92356301), Natural Science Foundation of Shanghai Municipality (21ZR1480400), Shanghai Municipal Science and Technology Major Project (Grant No. 2018SHZDZX03), the Program of Introducing Talents of Discipline to Universities (B16017), Scientific Committee of Shanghai (21JC1401700), the China Postdoctoral Science Foundation (2023TQ0118), Postdoctoral Fellowship Program of CPSF (GZB20230212), 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 high-resolution mass spectrometry (HRMS) analysis.

语种：英文

外文关键词：Carbon - Catalysis - Chemical bonds - Density functional theory - Enantioselectivity - Palladium - Stereochemistry

摘要：The development of a catalytic method for stereogenic carbon center formation holds immense significance in organic synthesis. Transition-metal-catalyzed cross-coupling reaction has been regarded as a straightforward and efficient tool for stereoselectively forging C-C bond. Nevertheless, the creation of acyclic all-carbon quaternary-containing vicinal stereocenters remains notoriously challenging within the domain of cross-coupling chemistry despite their prominence in various bioactive small molecules. Herein, we describe a palladium-catalyzed asymmetric multicomponent cross-coupling of trisubstituted alkene with aryl diazonium salts and arylboronic acids to realize the formation of tertiary-quaternary carbon centers with high regio-, distereo-, and enantioselectivity. Specifically, the precise manipulation of the stereoconfiguration of trisubstituted alkenes enables the divergent stereoselective cross-coupling reaction, thus allowing for the facile construction of all four enantiomers. Harnessing the ligand-swap strategy involving a chiral bisoxazoline and an achiral fumarate individually accelerates the enantioselective migratory insertion and reductive elimination step in the cross-coupling process, as supported by density functional theory (DFT) calculations, thus obviating the requirement for a neighboring directing group within the internal olefin skeleton.