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首页> 外文期刊>Catalysis science & technology >Insights into C-O insertion in a carbene/alkyne metathesis cascade reaction catalyzed by Rh-2(OAc)(4): a DFT study
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Insights into C-O insertion in a carbene/alkyne metathesis cascade reaction catalyzed by Rh-2(OAc)(4): a DFT study

机译：洞察切断插入碳烯/炔交换催化的级联反应DFT Rh-2 (OAc)(4):一个研究

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摘要

The reaction mechanisms of C-O insertion in the carbene/alkyne metathesis (CAM) cascade reaction of alkyne-tethered diazo compounds catalyzed by Rh-2(OAc)(4)are thoroughly studied with density functional theory (DFT) calculations. This is a detailed investigation into the CAM process, theoretical studies of which have rarely been reported before. The mechanism involves three key steps: CAM, cycloaddition and the H-transfer step, and thea prioriorder is the CAM step first, cycloaddition later and the H-transfer last. Meanwhile, the rate-determining step appears in the H-transfer step with a free energy barrier of 22.7 kcal mol(-1). Interestingly, our study suggests the final product can act as a catalyst to make the product form easily. The origins of the stereoselectivity and chemoselectivity of the catalytic reaction are investigated by distortion/interaction analysis, non-covalent interaction (NCI) analysis, and NBO calculations. It is the steric hindrance and weak interaction of the phenyl groups that control the stereoselectivity to generate theR-configuration product. In addition, the higher energy barrier of the 1,4-H transfer step makes the chemoselectivity more distinct.
机译：切断插入的反应机制碳烯/炔交换(CAM)级联反应的alkyne-tethered重氮的化合物催化Rh-2 (OAc)(4)彻底研究了密度泛函理论(DFT)计算。详细调查凸轮的过程,理论研究很少之前报道。步骤:凸轮,环加成作用和H-transferthea prioriorder是凸轮的一步一步,首先,环加成作用后,H-transfer持续。与此同时,速率决定步骤出现在自由能量势垒H-transfer步骤22.7千卡摩尔(1)。建议最终产品可以作为催化剂容易使产品形式。立体选择性和chemoselectivity催化反应研究失真/交互分析、非共价交互(NCI)分析和NBO计算。这是位阻和弱相互作用苯的组织控制立体选择性生成theR-configuration产品。1, 4 - h的转移步骤chemoselectivity更加明显。

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