Sandhiya Lakshmanan, Jangra Harish, Zipse Hendrik
Department of Chemistry, Ludwig-Maximilians-Universitaet Muenchen, Butenandtstrasse 5-13, 81377, Muenchen, Germany.
Angew Chem Int Ed Engl. 2020 Apr 16;59(16):6318-6329. doi: 10.1002/anie.201912382. Epub 2020 Feb 21.
Radical chain reactions are commonly initiated through the thermal or photochemical activation of purpose-built initiators, through photochemical activation of substrates, or through well-designed redox processes. Where radicals come from in the absence of these initiation strategies is much less obvious and are often assumed to derive from unknown impurities. In this situation, molecule-induced radical formation (MIRF) reactions should be considered as well-defined alternative initiation modes. In the most general definition of MIRF reactions, two closed-shell molecules react to give a radical pair or biradical. The exact nature of this transformation depends on the σ- or π-bonds involved in the MIRF process, and this Minireview specifically focuses on reactions that transform two σ-bonds into two radicals and a closed-shell product molecule.
自由基链式反应通常通过对特定引发剂进行热活化或光化学活化、对底物进行光化学活化或通过精心设计的氧化还原过程来引发。在没有这些引发策略的情况下，自由基的来源就不那么明显了，人们通常认为它们来自未知杂质。在这种情况下，分子诱导自由基形成（MIRF）反应应被视为明确的替代引发模式。在MIRF反应的最一般定义中，两个闭壳层分子反应生成一个自由基对或双自由基。这种转化的确切性质取决于MIRF过程中涉及的σ键或π键，本综述特别关注将两个σ键转化为两个自由基和一个闭壳层产物分子的反应。
