The pyridine-boryl radical chemistry has witnessed significant advancements in the last decade, enabling an array of novel synthetic applications. In this context, density functional theory calculations provide a computational mechanistic analysis of the pyridine/B₂pin₂-mediated cascade synthesis of indolizines. The radical–radical cross-coupling pathway is dissected to be energetically more feasible than the conventionally assumed Minisci-type radical addition route. Furthermore, the computations reveal that a 1,4-O[B] migration step leads to the formation of zwitterionic intermediates, whose cyclization then generates the indolizine scaffolds. H-shuttles, generated from water, alcohol, or amine molecules, are found to play pivotal roles in facilitating the elimination or aromatization processes.

中文翻译：

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吡啶-硼基自由基介导的中氮茚合成级联反应：计算机理分析


吡啶-硼基自由基化学在过去十年中取得了重大进展，实现了一系列新颖的合成应用。在这种情况下，密度泛函理论计算提供了吡啶/B ₂ pin ₂ 介导的中氮茚级联合成的计算机制分析。自由基-自由基交叉偶联途径被剖析为比传统假设的 Minisci 型自由基加成途径在能量上更可行。此外，计算表明 1,4-O[B] 迁移步骤导致两性离子中间体的形成，然后其环化生成中氮茚支架。由水、醇或胺分子产生的 H-梭被发现在促进消除或芳构化过程中发挥着关键作用。