This density functional theory (DFT) study explores the reaction mechanism of nickel-catalyzed hydroarylation of unactivated alkenes that selectively generates branched (Markovnikov) products. Extensive DFT calculations have revealed a novel and plausible mechanism via hydronickelation, which differs from the originally proposed pathway through carbonickelation. The N-heterocyclic carbene-anchored catalyst IPrNiOi-Pr favors β-hydride elimination from the alkoxide ligand over oxidative addition with carbon electrophiles. This chemoselectivity results in the formation of the Ni(I) hydride complex IPrNiH, initiating a hydronickelation pathway involving alkene into Ni–H insertion, PhOTf oxidative addition, and alkyl–phenyl reductive elimination. The β-hydride elimination represents the rate-limiting step, while the oxidative addition of PhOTf determines the regioselectivity, which is sterically controlled. This DFT study demonstrates a robust theoretical–experimental synergy and provides new mechanistic insights valuable for reaction development.

中文翻译：

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Ni（I） 催化的区域选择性烯烃加氢芳基化反应的机理见解：是碳镍化还是氢化镍化？


该密度泛函理论 （DFT） 研究探讨了镍催化的未活化烯烃加氢芳基化反应的反应机制，该氢化反应选择性地生成支链 （Markovnikov） 产物。广泛的 DFT 计算揭示了一种通过氢镍化的新颖且合理的机制，这与最初提出的通过碳镍化的途径不同。N-杂环卡宾锚定催化剂 IPrNiOi-Pr 比用亲碳电试剂氧化加成更有利于从醇盐配体中去除β氢化物。这种化学选择性导致 Ni（） 氢化物络合物 IPrNiH 的形成，启动了涉及烯烃到 Ni-H 插入、PhOTf 氧化加成和烷基-苯基还原消除的氢镍化途径。β-氢化物消除代表限速步骤，而 PhOTf 的氧化加成决定了区域选择性，这是空间控制的。这项 DFT 研究展示了强大的理论-实验协同作用，并为反应开发提供了有价值的新机理见解。