文献类型：期刊文献

英文题名：Nickel-catalysed regio- and stereoselective acylzincation of unsaturated hydrocarbons with organozincs and CO

作者：Weng, Yangyang[1,2];Zhang, Yetong[1,2];Turlik, Aneta[3];Wu, Xianqing[1,2];Li, Haiyan[1,2];Fei, Fan[1,2];Yao, Yongkang[1,2];Wang, Chenglong[1,2];Guo, Zhiqian[1,2];Qu, Jingping[1,2];Houk, K. N.[3];Chen, Yifeng[1,2]

机构：[1]East China Univ Sci & Technol, Frontiers Sci Ctr Materiobiol & Dynam Chem, Sch Chem & Mol Engn, Key Lab Adv Mat,Feringa Nobel Prize Scientist Join, Shanghai, 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, Peoples R China;[3]Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA

年份：2023

卷号：2

期号：3

起止页码：261

外文期刊名：NATURE SYNTHESIS

收录：WOS:【ESCI(收录号:WOS:001124815300007)】；

基金：This work was supported by NSFC/China (grant nos. 21702060 and 22171079), the National Science Foundation (grant no. CHE-1764328), Natural Science Foundation of Shanghai (grant no. 21ZR1480400), Shanghai Rising-Star Program (grant no. 20QA1402300), Shanghai Municipal Science and Technology Major Project (grant no. 2018SHZDZX03), the Program of Introducing Talents of Discipline to Universities (grant no. B16017), the Fundamental Research Funds for the Central Universities and the China Postdoctoral Science Foundation (grant no. 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 no. OCI-1053575). We thank the Analysis and Testing Center of East China University of Science and Technology for help with NMR spectroscopy analysis.

语种：英文

摘要：Carbometallation of unsaturated hydrocarbons is one of the most straightforward functionalizations of carbon-carbon unsaturated bonds; however, the analogous acylmetallation remains a significant synthetic challenge. Here, we disclose the nickel-catalysed acylzincation of ynamides, oxabicyclic alkenes and alpha,beta-unsaturated ketones with organozinc reagents under 1 atm of CO, featuring excellent functional group tolerance, a broad substrate scope and mild conditions. The acyl functionality generated in situ from an organozinc reagent can be viewed as a nucleophilic synthon, and the corresponding acylzincation intermediate is trapped via intermolecular reaction with electrophiles. Alternatively, the intermediate can undergo an intramolecular Truce-Smiles rearrangement or aldol condensation to afford tetrasubstituted enones, multisubstituted benzocyclohexane derivatives and cyclopentenones. This method is applied to the formal synthesis of the anthracyclinone antibiotic daunomycinone, as well as to prepare functionalized 1,3-dienones possessing aggregation-induced emission activity. The syn metallation of acyl nickel intermediates with unsaturated hydrocarbons allows for the complete regioselective and highly stereoselective formation of functionalized zinc intermediates. Furthermore, density functional theory calculations show that acylmetallation is lower in energy than alkylmetallation, and demonstrates that favourable interaction energies lead to a lower energy transition state for formation of the major regioisomer. The use of acyl functional groups as nucleophilic synthons in transition metal-catalysed carbometallation of unsaturated hydrocarbons remains challenging. Here, nickel-catalysed acylzincation reactions of alkynes and alkenes with organozinc reagents under 1 atm of CO are developed, featuring high functional group tolerance, a broad substrate scope and mild conditions.