Zhang Zeyu, Li Jiayuan, Xi Chanjuan
MOE Laboratory of Bioorganic Phosphorus Chemistry & Chemical Biology, Department of Chemistry, Tsinghua University, Beijing 100084, People's Republic of China.
State Key Laboratory of Elemento Organic Chemistry, Nankai University, Tianjin 300071, People's Republic of China.
Org Lett. 2023 Nov 17;25(45):8178-8182. doi: 10.1021/acs.orglett.3c03528. Epub 2023 Nov 7.
CO-assisted and Ni-catalyzed direct reductive allylation of aldehydes utilizing allylic alcohols as allylic precursor has been reported. Various homoallyl alcohols could be synthesized in excellent yield with enhanced regioselectivity and stereoselectivity for alkyl- and aryl-substituted aldehydes under mild conditions. For different substrates, proper collocation of the catalytic precursor and ligand is crucial. Preliminary mechanistic studies supported the reaction pathway through a sequential allyl hydrocarbonate formation/allylnickelation/coordination insertion process by the Ni(I)/Ni(III) catalytic cycle, which has been proven by cyclic voltammetry analysis.
据报道，利用烯丙醇作为烯丙基前体，通过一氧化碳辅助和镍催化实现醛的直接还原烯丙基化反应。在温和条件下，对于烷基和芳基取代的醛，可以以优异的产率合成各种高烯丙醇，同时区域选择性和立体选择性得到增强。对于不同的底物，催化前体和配体的适当搭配至关重要。初步机理研究支持了通过镍（I）/镍（III）催化循环依次形成烯丙基碳酸酯/烯丙基镍化/配位插入过程的反应途径，这已通过循环伏安分析得到证实。
