通过 PCET 激活强 O-H 键实现环状醇的催化开环。
Catalytic Ring-Opening of Cyclic Alcohols Enabled by PCET Activation of Strong O-H Bonds.
机构信息
Department of Chemistry, Princeton University , Princeton, New Jersey 08544, United States.
出版信息
J Am Chem Soc. 2016 Aug 31;138(34):10794-7. doi: 10.1021/jacs.6b06517. Epub 2016 Aug 18.
Abstract
We report a new photocatalytic protocol for the redox-neutral isomerization of cyclic alcohols to linear ketones via C-C bond scission. Mechanistic studies demonstrate that key alkoxy radical intermediates in this reaction are generated via the direct homolytic activation of alcohol O-H bonds in an unusual intramolecular PCET process, wherein the electron travels to a proximal radical cation in concert with proton transfer to a weak Brønsted base. Effective bond strength considerations are shown to accurately forecast the feasibility of alkoxy radical generation with a given oxidant/base pair.
摘要
我们报告了一种新的光催化协议，用于通过 C-C 键断裂将环状醇氧化还原中性异构化为线性酮。 机理研究表明，该反应中的关键烷氧基自由基中间体是通过在不寻常的分子内 PCET 过程中直接均裂醇 O-H 键生成的，其中电子与质子转移到弱布朗斯台德碱一起转移到邻近的自由基阳离子。 有效键强度的考虑因素被证明可以准确预测给定氧化剂/碱对生成烷氧基自由基的可行性。
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