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Redox-Tag Processes: Intramolecular Electron Transfer and Its Broad Relationship to Redox Reactions in General
Chemical Reviews ( IF 62.1 ) Pub Date : 2017-12-08 00:00:00 , DOI: 10.1021/acs.chemrev.7b00400
Yohei Okada 1 , Kazuhiro Chiba 2
Affiliation  

Explosive growth in the use of open shell reactivity, including neutral radicals and radical ions, in the field of synthetic organic chemistry has been observed in the past decade, particularly since the advent of ruthenium complexes in 2008. These complexes generally induce single-electron transfer (SET) processes via visible-light absorption. Additionally, recent significant advancements in organic electrochemistry involving SET processes to provide open shell reactivity offer a complementary method to traditional polarity-driven reactions described by two-electron transfer processes. In this Review, we highlight the importance of intramolecular SET processes in the field of synthetic organic chemistry, which seem to be more elusive than the intermolecular versions, since they are net redox-neutral and thus cannot simply be regarded as oxidations or reductions. Such intramolecular SET processes can rationally be understood in combination with concomitant bond formations and/or cleavages, and are regulated by a structural motif that we call a “redox tag.” In order to describe modern radical-driven reactions involving SET processes, we focus on a classical formalism in which electrons are treated as particles rather than waves, which offers a practical yet powerful approach to explain and/or predict synthetic outcomes.

中文翻译:

氧化还原标签过程:分子内电子转移及其与一般氧化还原反应的广泛关系

在过去的十年中,特别是自2008年钌络合物问世以来,人们观察到在合成有机化学领域中使用开壳反应性(包括中性自由基和自由基离子)的爆炸性增长。这些络合物通常会诱导单电子转移(SET)通过可见光吸收进行处理。另外,涉及SET过程以提供开壳反应性的有机电化学的最新重大进展为由双电子转移过程描述的传统的极性驱动反应提供了一种补充方法。在这篇综述中,我们强调了分子内SET过程在合成有机化学领域中的重要性,这似乎比分子间的过程更难以捉摸。因为它们是净氧化还原中性的,因此不能简单地视为氧化或还原。可以结合结合的键形成和/或裂解来合理地理解此类分子内SET过程,并受我们称为“氧化还原标签”的结构基序调节。为了描述涉及SET过程的现代自由基驱动的反应,我们关注经典的形式主义,在这种形式主义中,电子被视为粒子而不是波,这提供了一种实用而强大的方法来解释和/或预测合成结果。
更新日期:2017-12-08
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