Recent research has developed a Cu/Ru dual catalysis system for the hydroalkylation of racemic allylic alcohols and racemic ketimine esters. This method is distinguished by its ability to stereodivergently generate 1,4-nonadjacent stereocenters. This study employs density functional theory calculations to elucidate how copper and ruthenium synergistically drive this transformation and to reveal why this dual-catalyst system is more efficient than systems using either copper or ruthenium independently. The findings show how different combinations of chiral catalysts influence the formation of two stereogenic centers. We highlight the critical roles of noncovalent interactions and steric effects in determining the most energetically favorable transition states for each catalyst combination. Additionally, this study elucidates the significant role of potassium phosphate (K₃PO₄) in enhancing the reaction efficiency. Specifically, K₃PO₄ facilitates the dehydrogenation and hydrogenation processes across all three stages of the catalytic cycle. We also explore the reaction's chemoselectivity by computing the formation mechanisms of three potential by-products and analyzing the driving forces behind the generation of the desired product. These mechanistic insights can support advancements in stereodivergent synthesis using cooperative bimetallic catalysis.

中文翻译：

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铜/钌中继催化用于 1,4-不相邻立体中心的立体发散构建：使用 DFT 计算进行机理研究


最近的研究开发了一种用于外消旋烯丙醇和外消旋酮亚胺酯加氢烷基化的Cu/Ru双催化系统。该方法的特点是能够立体发散地生成 1,4-不相邻立体中心。这项研究采用密度泛函理论计算来阐明铜和钌如何协同驱动这种转变，并揭示为什么这种双催化剂系统比单独使用铜或钌的系统更有效。研究结果表明手性催化剂的不同组合如何影响两个立体中心的形成。我们强调非共价相互作用和空间效应在确定每种催化剂组合最有利的过渡态方面的关键作用。此外，本研究阐明了磷酸钾 (K ₃ PO ₄ ) 在提高反应效率方面的重要作用。具体而言，K ₃ PO ₄ 促进催化循环所有三个阶段的脱氢和加氢过程。我们还通过计算三种潜在副产物的形成机制并分析所需产物生成背后的驱动力来探索反应的化学选择性。这些机制见解可以支持使用协同双金属催化的立体发散合成的进展。