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- Dirk Leifert
- Organisch-Chemisches Institut Westfälische Wilhelms-Universität Corrensstraße 40 48149 Münster Germany
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- Armido Studer
- Key Laboratory of Coal to Ethylene Glycol and Its Related Technology State Key Laboratory of Structural Chemistry Center for Excellence in Molecular Synthesis Fujian Institute of Research on the Structure of Matter Chinese Academy of Sciences 155 Yangqiao Road West Fuzhou Fujian 350002 P. R. China
書誌事項
- 公開日
- 2019-10-31
- 権利情報
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- http://onlinelibrary.wiley.com/termsAndConditions#vor
- DOI
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- 10.1002/anie.201903726
- 公開者
- Wiley
この論文をさがす
説明
<jats:title>Abstract</jats:title><jats:p>Radical–radical couplings are mostly nearly diffusion‐controlled processes. Therefore, the selective cross‐coupling of two different radicals is challenging and not a synthetically valuable transformation. However, if the radicals have different lifetimes and if they are generated at equal rates, cross‐coupling will become the dominant process. This high cross‐selectivity is based on a kinetic phenomenon called the persistent radical effect (PRE). In this Review, an explanation of the PRE supported by simulations of simple model systems is provided. Radical stabilities are discussed within the context of their lifetimes, and various examples of PRE‐mediated radical–radical couplings in synthesis are summarized. It is shown that the PRE is not restricted to the coupling of a persistent with a transient radical. If one coupling partner is longer‐lived than the other transient radical, the PRE operates and high cross‐selectivity is achieved. This important point expands the scope of PRE‐mediated radical chemistry. The Review is divided into two parts, namely 1) the coupling of persistent or longer‐lived organic radicals and 2) “radical–metal crossover reactions”; here, metal‐centered radical species and more generally longer‐lived transition‐metal complexes that are able to react with radicals are discussed—a field that has flourished recently.</jats:p>
収録刊行物
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- Angewandte Chemie International Edition
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Angewandte Chemie International Edition 59 (1), 74-108, 2019-10-31
Wiley
