Wang Zi-Chao, Zhang Jia-Wen, Koh Ming Joo, Shi Shi-Liang
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, P. R. China.
Department of Chemistry, National University of Singapore, 4 Science Drive 2, Singapore, 117544, Republic of Singapore.
Angew Chem Int Ed Engl. 2023 Nov 6;62(45):e202310203. doi: 10.1002/anie.202310203. Epub 2023 Oct 2.
Light olefins are abundantly manufactured in the petroleum industry and thus represent ideal starting materials for modern chemical synthesis. Selective and divergent transformations of feedstock light olefins to value-added chemicals are highly sought-after but remain challenging. Herein we report an exceptionally regioselective carbonickelation of light alkenes followed by in situ trapping with three types of nucleophiles, namely a reductant, base, or Grignard reagent. This protocol enables efficient 1,2-hydrofunctionalization, dicarbofunctionalization, and branched-selective Heck-type cross-coupling of light alkenes with aryl and alkenyl reagents to streamline access to diverse alkyl arenes and complex alkenes. Harnessing bulky N-heterocyclic carbene ligands with acenaphthyl backbones for nickel catalysts is crucial to attain high reactivity and selectivity. This strategy provides a rare, modular, and divergent platform for upgrading feedstock alkenes and is expected to find broad applications in medicinal chemistry and industrial processes.
轻质烯烃在石油工业中大量生产，因此是现代化学合成的理想起始原料。将原料轻质烯烃选择性地转化为高附加值化学品极具吸引力，但仍具有挑战性。在此，我们报道了一种对轻质烯烃具有异常区域选择性的碳镍化反应，随后用三种亲核试剂进行原位捕获，这三种亲核试剂分别是还原剂、碱或格氏试剂。该方法能够实现轻质烯烃与芳基和烯基试剂的高效1,2-氢官能化、双碳官能化以及支链选择性Heck型交叉偶联反应，从而简化了获取各种烷基芳烃和复杂烯烃的过程。使用具有苊基骨架的大位阻N-杂环卡宾配体作为镍催化剂对于实现高反应活性和选择性至关重要。该策略为升级原料烯烃提供了一个罕见的、模块化的且多样化的平台，有望在药物化学和工业过程中得到广泛应用。
