The Institute for Advanced Studies (IAS), Wuhan University, Wuhan 430072, P. R. China.
Engineering Research Center of Organosilicon Compounds & Materials, Ministry of Education, College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, P. R. China.
J Am Chem Soc. 2022 Jan 26;144(3):1389-1395. doi: 10.1021/jacs.1c11791. Epub 2021 Dec 29.
Selective hydrogenation of epoxides would be a direct and powerful approach for alcohol synthesis, but it has proven to be elusive. Here, electrochemically epoxide hydrogenation using electrons and protons as reductants is reported. A wide range of primary, secondary, and tertiary alcohols can be achieved through selective Markovnikov or anti-Markovnikov ring opening in the absence of transition metals. Mechanistic investigations revealed that the regioselectivity is controlled by the thermodynamic stabilities of the in situ generated benzyl radicals for aryl-substituted epoxides and the kinetic tendency for Markovnikov selective ring opening for alkyl-substituted epoxides.
环氧化物的选择性加氢是一种直接且强大的醇合成方法，但事实证明这是难以实现的。在此，我们报告了使用电子和质子作为还原剂的电催化环氧化物加氢。在没有过渡金属的情况下，可以通过选择性的马氏规则或反马氏规则开环，实现伯醇、仲醇和叔醇的合成。机理研究表明，区域选择性由芳基取代环氧化物原位生成的苄基自由基的热力学稳定性以及烷基取代环氧化物的马氏规则选择性开环的动力学趋势控制。
