With metal or not? a computationally predicted rule for a dirhodium catalyst in [3+3] cycloadditions of triazole with thiirane

A mixture of pathways including the use of catalyst was proposed for a dirhodium-mediated triazole activation-cycloaddition. This proposal was supported by the results of density functional theory (DFT) calculations, and was indicated to involve a non-catalyzed cleavage of the triazole N-N bond foll...

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Bibliographic Details
Published inChemical communications (Cambridge, England) Vol. 56; no. 34; pp. 4732 - 4735
Main Authors Li, Shi-Jun, Li, Xue, Mo, Huilin, Qu, Ling-Bo, Wei, Donghui, Lan, Yu
Format Journal Article
LanguageEnglish
Published England Royal Society of Chemistry 30.04.2020
Subjects
Carboxylates
Catalysts
catalytic activity
chemical bonding
Cycloaddition
cycloaddition reactions
Denitrogenation
Density functional theory
Enthalpy
Mathematical analysis
Triazoles
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ISSN1359-7345
1364-548X
1364-548X
DOI10.1039/d0cc01293a

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Summary:A mixture of pathways including the use of catalyst was proposed for a dirhodium-mediated triazole activation-cycloaddition. This proposal was supported by the results of density functional theory (DFT) calculations, and was indicated to involve a non-catalyzed cleavage of the triazole N-N bond followed by a dirhodium-assisted denitrogenation. Electron-deficient carboxylates were found to be favourable for the rate-determining denitrogenation step. Three possible pathways were explored to determine the inherent role of dirhodium in triazole transformation/functionalization.
Bibliography:10.1039/d0cc01293a
Electronic supplementary information (ESI) available: Computational details; the DFT-calculated geometries for all stationary points along reactions studied; total electronic energies, enthalpies, entropies and free energies. See DOI
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ISSN:1359-7345
1364-548X
1364-548X
DOI:10.1039/d0cc01293a