Transition metal catalyzed difunctionalization reactions of alkenes using simple chemical feedstocks are powerful strategies for the synthesis of valuable compounds and materials. Density functional theory (DFT) calculations reported in the present paper reveal detailed mechanistic insight and the origin of the substrate-dependent regioselectivity in the titled reactions. Computational results demonstrate that these reactions are generally composed of several steps including oxidative addition, carbonickelation, H-shift/transmetalation, and reductive elimination. Among these steps, the key one responsible for the regioselectivity depends upon the organic halides utilized. Natural bond orbital (NBO) analysis, energy decomposition analysis (EDA), and buried volume calculations indicate that steric effect is a common contributor of the regioselectivity, while other energy terms, such as electrostatic interaction, have significant and even dominant effects on the specific regioselectivity. Furthermore, the key reason for successfully suppressing Heck and/or Suzuki products lies in that the formation of Heck and/or Suzuki products is thermodynamically less favorable. Comparison of the total reaction barriers of the rate-limiting step (combined transmetalation and reductive elimination processes) demonstrates that the electron-induced effect of various organic halides significantly causes the different bonding ability between Ni atom and allyl moiety. As a result, transmetalation and reductive elimination processes made distinct contributions to reducing the total activation free energy of the rate-limiting step of various difunctionalized reactions.

中文翻译：

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机械观察到的使用有机硼酸和有机卤化物进行镍催化的烯烃双官能化的机理：了解显着的底物依赖性区域选择性

使用简单的化学原料，烯烃的过渡金属催化的双官能化反应是合成有价值的化合物和材料的强大策略。本文中报道的密度泛函理论（DFT）计算揭示了详细的机理研究以及标题反应中底物依赖性区域选择性的起源。计算结果表明，这些反应通常由几个步骤组成，包括氧化加成，羰基化，H移/重金属化和还原消除。在这些步骤中，引起区域选择性的关键因素取决于所使用的有机卤化物。自然键轨道（NBO）分析，能量分解分析（EDA），埋藏量的计算表明，空间效应是区域选择性的共同贡献者，而其他能量项（例如静电相互作用）对比区域选择性具有显着甚至主导的影响。此外，成功抑制Heck和/或Suzuki产物的关键原因在于Heck和/或Suzuki产物的形成在热力学上是不利的。限速步骤（结合的过渡金属化和还原消除过程）的总反应势垒的比较表明，各种有机卤化物的电子诱导效应显着导致了Ni原子与烯丙基之间的不同键合能力。结果是，