In this comment, insights gained from density functional theory into the mechanism by which the Cu(I)-catalyzed boracarboxylation of vinyl arenes occurs with specific focus on the CO₂ insertion step are presented. Preliminary calculations indicated a potential non-covalent interaction between boron and CO₂ in the carboxylation transition state, implicating cooperative CO₂ activation. A study of boron Lewis acidity was conducted through substitution of sp² mono-boron substituents. An inverse correlation between boron valence deficiency (BVD) and the enthalpic barrier of CO₂ insertion into the β-borylbenzyl-Cu(I) bond was revealed, supporting Lewis acid/base cooperativity between boron and the proximal oxygen of CO₂ at the carboxylation insertion transition state. These findings suggest that future methodology development should consider strategic incorporation of similar Lewis acidic functionality to facilitate carboxylation of challenging substrates.

在这篇评论中，我们从密度泛函理论中获得了对Cu（I）催化的乙烯基芳烃硼酸酯化反应机理的见解，并特别侧重于CO ₂插入步骤。初步计算表明，在羧化过渡态下硼和CO ₂之间可能存在非共价相互作用，这意味着协同CO ₂活化。通过取代sp ²单硼取代基来进行硼路易斯酸度的研究。硼价缺乏（BVD）与CO ₂的焓屏障成反比揭示了在β-硼基苄基-Cu（I）键中的插入，从而支持了在羧基化插入过渡态下硼与CO ₂的近端氧之间的路易斯酸/碱协同作用。这些发现表明，未来的方法开发应考虑战略性地引入相似的路易斯酸性官能团，以促进具有挑战性的底物的羧化。