Okamoto Kazuhiro, Shida Naoki, Atobe Mahito
Graduate School of Engineering, Yokohama National University, 79-7 Tokiwadai, Hodogaya-ku, Yokohama, Kanagawa 240-8501, Japan.
Beilstein J Org Chem. 2024 Feb 12;20:264-271. doi: 10.3762/bjoc.20.27. eCollection 2024.
Electrochemically generated amidyl radical species produced distinct inter- or intramolecular hydroamination reaction products via a proton-coupled electron transfer (PCET) mechanism. Cyclic voltammetry (CV) analysis indicated that the chemoselectivity was derived from the size of the hydrogen bond complex, which consisted of the carbamate substrate and phosphate base, and could be controlled using 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) as an additive. These results provide fundamental insights for the design of PCET-based redox reaction systems under electrochemical conditions.
通过质子耦合电子转移（PCET）机制，电化学产生的酰胺基自由基物种生成了不同的分子间或分子内氢胺化反应产物。循环伏安法（CV）分析表明，化学选择性源自由氨基甲酸酯底物和磷酸碱基组成的氢键复合物的大小，并且可以使用1,1,1,3,3,3-六氟-2-丙醇（HFIP）作为添加剂来控制。这些结果为电化学条件下基于PCET的氧化还原反应体系的设计提供了基本见解。
