Mechanism of Iron-Catalyzed C—H Alkenylation of Pivalophenone Derivatives With Unsymmetric Internal Alkynes

IF 2.3 3区 化学 Q3 CHEMISTRY, PHYSICAL International Journal of Quantum Chemistry Pub Date : 2024-09-11 DOI:10.1002/qua.27479
Stefano Santoro
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Abstract

The mechanism of an iron-catalyzed C—H alkenylation of pivalophenone derivatives with unsymmetric internal alkynes is investigated in details by means of density functional theory calculations. It is shown that the reaction begins with two consecutive ligand exchanges, followed by a fast and reversible oxidative addition C—H activation step. Next, an alkyne insertion into the Fe—H bond, two isomerization steps, and a reductive elimination afford the final product. The reductive elimination is the turnover-limiting step of the process, and also determines the regiochemical outcome of the reaction. The origin of the regioselectivity is proposed to be the steric repulsion between the bulky trimethylsilyl group and the aromatic fragment in the reductive elimination step leading to the not observed regioisomer.

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铁催化具有不对称内部炔烃的新戊酮衍生物的 C-H 烯化机理
通过密度泛函理论计算,详细研究了铁催化的具有不对称内部炔烃的新戊酮衍生物 C-H 烯化反应的机理。结果表明,反应开始于两个连续的配体交换,然后是快速、可逆的氧化加成 C-H 活化步骤。接着,炔烃插入 Fe-H 键、两个异构化步骤和还原消除步骤产生最终产物。还原消除是该过程中限制转化率的步骤,也决定了反应的区域化学结果。这种区域选择性的起源被认为是在还原消除步骤中,笨重的三甲基硅基与芳香族片段之间的立体排斥导致了未观察到的区域异构体。
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来源期刊
International Journal of Quantum Chemistry
International Journal of Quantum Chemistry 化学-数学跨学科应用
CiteScore
4.70
自引率
4.50%
发文量
185
审稿时长
2 months
期刊介绍: Since its first formulation quantum chemistry has provided the conceptual and terminological framework necessary to understand atoms, molecules and the condensed matter. Over the past decades synergistic advances in the methodological developments, software and hardware have transformed quantum chemistry in a truly interdisciplinary science that has expanded beyond its traditional core of molecular sciences to fields as diverse as chemistry and catalysis, biophysics, nanotechnology and material science.
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