文献类型：期刊文献

英文题名：Nickel-catalyzed allylic carbonylative coupling of alkyl zinc reagents with tert-butyl isocyanide

作者：Weng, Yangyang[1,2,3];Zhang, Chenhuan[1,2,3];Tang, Zaiquan[1,2,3];Shrestha, Mohini[1,2,3];Huang, Wenyi[1,2,3];Qu, Jingping[1,2,3];Chen, Yifeng[1,2,3]

机构：[1]East China Univ Sci & Technol, Sch Chem & Mol Engn, Feringa Nobel Prize Scientist Joint Res Ctr, Key Lab Adv Mat, 130 Meilong Rd, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Key Lab Adv Mat, Sch Chem & Mol Engn, Feringa Nobel Prize Scientist Joint Res Ctr, 130 Meilong Rd, Shanghai 200237, Peoples R China;[3]East China Univ Sci & Technol, Sch Chem & Mol Engn, Feringa Nobel Prize Scientist Joint Res Ctr, Joint Int Res Lab Precis Chem & Mol Engn, 130 Meilong Rd, Shanghai 200237, Peoples R China

年份：2020

卷号：11

期号：1

外文期刊名：NATURE COMMUNICATIONS

收录：;WOS:【SCI-EXPANDED(收录号:WOS:000512537400013)】；

基金：This work was supported by the Youth 1000-Talent Plan Program, East China University of Science and Technology for startup funding, NSFC/China (21421004, 21702060), Shanghai Municipal Science and Technology Major Project (grant no. 2018SHZDZX03) and the Program of Introducing Talents of Discipline to Universities (B16017), and the Fundamental Research Funds for the Central Universities (WJ1814012). We thank Research Center of Analysis and Test of East China University of Science and Technology for the help on NMR analysis. Y.C. thanks Dr. Yang Yang (California Institute of Technology) in proofreading this manuscript.

语种：英文

摘要：Transition metal-catalyzed carbonylation with carbon nucleophiles is one of the most prominent methods to construct ketones, which are highly versatile motifs prevalent in a variety of organic compounds. In comparison to the well-established palladium catalytic system, the nickel-catalyzed carbonylative coupling is much underdeveloped due to the strong binding affinity of CO to nickel. By leveraging easily accessible tert-butyl isocyanide as the CO surrogate, we present a nickel-catalyzed allylic carbonylative coupling with alkyl zinc reagent, allowing for the practical and straightforward preparation of synthetically important beta,gamma-unsaturated ketones in a linear-selective fashion with excellent trans-selectivity under mild conditions. Moreover, the undesired polycarbonylation process which is often encountered in palladium chemistry could be completely suppressed. This nickel-based method features excellent functional group tolerance, even including the active aryl iodide functionality to allow the orthogonal derivatization of beta,gamma-unsaturated ketones. Preliminary mechanistic studies suggest that the reaction proceeds via a pi-allylnickel intermediate.