Models for Understanding Divergent Reactivity in Lewis Acid-Catalyzed Transformations of Carbonyls and Olefins,ACS Catalysis

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Models for Understanding Divergent Reactivity in Lewis Acid-Catalyzed Transformations of Carbonyls and Olefins
ACS Catalysis ( IF 11.3 ) Pub Date : 2020-03-25 , DOI: 10.1021/acscatal.0c00489
Marc R. Becker ₁ , Jolene P. Reid ₂ , Katie A. Rykaczewski ₁ , Corinna S. Schindler ₁

Affiliation

Carbonyl–ene, Prins, and carbonyl–olefin metathesis reactions represent powerful strategies for carbon–carbon bond formation relying on Lewis acid catalysts. Although common Lewis acids are able to provide efficient activation, the reactions often proceed with low regio- or chemoselectivity, while high selectivity frequently requires the use of well-designed metal–ligand complexes. Here we demonstrate that simple Lewis acids including Me₂AlCl, FeCl₃, and SnCl₄ can show remarkable selectivity in differentiating between distinct transformations of carbonyl and olefin functional groups, resulting in either carbonyl–ene or carbonyl–olefin metathesis products. Specifically, we report the development of predictive multivariate linear regression models that rely on kinetic and thermodynamic information obtained in DFT calculations to gain important insights into the complex potential energy surfaces (PES) of these competing reaction paths. The presented results further our understanding of Lewis acid reactivity and suggest that even simple Lewis acids have the potential to function as highly selective catalysts.

中文翻译：

路易斯酸催化的羰基和烯烃转化反应中不同反应性的模型

羰基烯烃，普林斯和羰基烯烃的复分解反应代表了依靠路易斯酸催化剂形成碳碳键的强大策略。尽管常见的路易斯酸能够提供有效的活化作用，但反应通常在低区域选择性或化学选择性的情况下进行，而高选择性经常需要使用设计良好的金属-配体络合物。在这里，我们证明了简单的路易斯酸，包括Me ₂ AlCl，FeCl ₃和SnCl ₄在区分羰基和烯烃官能团的不同转化时可以显示出显着的选择性，从而产生羰基烯烃或羰基烯烃复分解产物。具体而言，我们报告了预测多元线性回归模型的开发，该模型依赖于DFT计算中获得的动力学和热力学信息，以获取对这些竞争反应路径的复杂势能面（PES）的重要见解。提出的结果进一步加深了我们对路易斯酸反应性的理解，并表明即使是简单的路易斯酸也有可能充当高选择性催化剂。

更新日期：2020-03-26

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