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