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有机光氧化还原催化的苄醇单分子质子耦合电子转移反应

Organic photoredox-catalyzed unimolecular PCET of benzylic alcohols.

作者信息

Matsuo Tomotoki, Sano Masaki, Sumida Yuto, Ohmiya Hirohisa

机构信息

Institute for Chemical Research, Kyoto University Gokasho Uji Kyoto 611-0011 Japan

Division of Pharmaceutical Sciences, Graduate School of Medical Sciences, Kanazawa University Kakuma-machi Kanazawa 920-1192 Japan.

出版信息

Chem Sci. 2025 Jan 8;16(7):3150-3156. doi: 10.1039/d4sc07048h. eCollection 2025 Feb 12.

DOI:10.1039/d4sc07048h
PMID:39829983
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11740339/
Abstract

Proton-coupled electron transfer (PCET) is a crucial chemical process involving the simultaneous or sequential transfer of protons and electrons, playing a vital role in biological processes and energy conversion technologies. This study investigates the use of an organic photoredox catalyst to facilitate a unimolecular PCET process for the generation of alkyl radicals from benzylic alcohols, with a particular focus on alcohols containing electron-rich arene units. By employing a benzophenone derivative as the catalyst, the reaction proceeds efficiently under photoirradiation, achieving significant yields without the need for a Brønsted base. The findings highlight the potential of this unimolecular PCET mechanism to streamline radical generation in organic synthesis, offering a more efficient and flexible alternative to conventional methods.

摘要

质子耦合电子转移(PCET)是一个关键的化学过程,涉及质子和电子的同时或顺序转移,在生物过程和能量转换技术中起着至关重要的作用。本研究考察了使用有机光氧化还原催化剂来促进单分子PCET过程,以从苄醇生成烷基自由基,特别关注含有富电子芳烃单元的醇。通过使用二苯甲酮衍生物作为催化剂,该反应在光照射下有效进行,无需布朗斯特碱即可获得显著产率。这些发现突出了这种单分子PCET机制在简化有机合成中自由基生成方面的潜力,为传统方法提供了一种更高效、更灵活的替代方案。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/128e/11818128/5164474eef79/d4sc07048h-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/128e/11818128/9ceb86f8cc90/d4sc07048h-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/128e/11818128/9111bdc06cb3/d4sc07048h-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/128e/11818128/c5140ec9fba5/d4sc07048h-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/128e/11818128/5164474eef79/d4sc07048h-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/128e/11818128/9ceb86f8cc90/d4sc07048h-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/128e/11818128/9111bdc06cb3/d4sc07048h-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/128e/11818128/c5140ec9fba5/d4sc07048h-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/128e/11818128/5164474eef79/d4sc07048h-f4.jpg

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Multiplicative enhancement of stereoenrichment by a single catalyst for deracemization of alcohols.
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Photochemical and Electrochemical Applications of Proton-Coupled Electron Transfer in Organic Synthesis.质子耦合电子转移在有机合成中的光化学和电化学应用。
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Iron-Catalyzed C-C Single-Bond Cleavage of Alcohols.铁催化醇的碳-碳单键裂解
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