用DFT研究[VO(acac)2]催化酸功能化对烯烃功能化的机理

IF 2.7 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta Pub Date : 2025-05-08 DOI:10.1016/j.ica.2025.122750

Fathima Febin Koothradan, Vikiho Wotsa, Payyeri Krishna, P. P. Hiba Sherin, Chinnappan Sivasankar

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引用次数: 0

摘要

化学选择性反应通过在复杂分子中选择性地针对不同的官能团而不是潜在的替代品来促进有机合成的精确控制。本文从实验和理论上分析了[VO(acac)2]-催化的化学选择性酸功能化对环丙烷化和ch功能化的影响。本文报道了我们为深入研究钒基催化的碳插入反应机理所做的努力。采用密度泛函理论（DFT）对[VO(acac)2]-催化酸功能化的各种假定反应途径进行了仔细研究，以发现最可能的机理。随后，通过DFT分析比较了酸官能化、环丙烷化、ch官能化和芳香ch官能化的催化循环，发现酸官能化的能量势垒最低，支持化学选择性酸官能化优于烯烃官能化。

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Mechanistic investigation of the [VO(acac)2]-catalyzed acid-functionalization over olefin-functionalization using DFT studies

Chemoselective reactions facilitate precise control in organic synthesis by selectively targeting distinct functional groups over potential alternatives within complex molecules. In this work, [VO(acac)₂]-catalyzed chemoselective acid-functionalization over cyclopropanation and CH-functionalization are analyzed experimentally and theoretically. This paper reports our efforts to delve deeper into the mechanisms of vanadyl-catalyzed carbene insertion reactions. Density functional theory (DFT) was used to scrutinize various putative reaction pathways for [VO(acac)₂]-catalyzed acid-functionalization to discover the most likely mechanism. Afterward, catalytic cycles of acid-functionalization, cyclopropanation, CH-functionalization, and aromatic CH-functionalization were compared using DFT analysis, and we observed the lowest energy barrier for acid functionalization, which supported the chemoselective acid functionalization over olefin-functionalization.

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来源期刊

Inorganica Chimica Acta 化学-无机化学与核化学

CiteScore

6.00

自引率

3.60%

发文量

440

审稿时长

35 days

期刊介绍： Inorganica Chimica Acta is an established international forum for all aspects of advanced Inorganic Chemistry. Original papers of high scientific level and interest are published in the form of Articles and Reviews. Topics covered include: • chemistry of the main group elements and the d- and f-block metals, including the synthesis, characterization and reactivity of coordination, organometallic, biomimetic, supramolecular coordination compounds, including associated computational studies; • synthesis, physico-chemical properties, applications of molecule-based nano-scaled clusters and nanomaterials designed using the principles of coordination chemistry, as well as coordination polymers (CPs), metal-organic frameworks (MOFs), metal-organic polyhedra (MPOs); • reaction mechanisms and physico-chemical investigations computational studies of metalloenzymes and their models; • applications of inorganic compounds, metallodrugs and molecule-based materials. Papers composed primarily of structural reports will typically not be considered for publication.