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1,3 Dipolar Cycloaddition of Münchnones: Factors behind the Regioselectivity
Ist Teil von
The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, 2023-01, Vol.127 (3), p.645-660
Ort / Verlag
United States
Erscheinungsjahr
2023
Quelle
Alma/SFX Local Collection
Beschreibungen/Notizen
The 1,3 dipolar cycloaddition reactions of münchnones and alkenes provide an expedite synthetic way to substituted pyrroles, an exceedingly important structural motif in the pharmaceutical and material science fields of research. The factors governing their regioselectivity rationalization are not well understood. Using several approaches, we investigate a set of 14 reactions (featuring two münchnones, 12 different alkenes, and two alkynes). The Natural Bond Theory and the Non-Covalent Interaction Index analyses of the noncovalent interaction energies fail to predict the experimental major regioisomer. Employing global cDFT descriptors or local ones such as the Fukui function and dual descriptor yields similarly inaccurate predictions. Only the local softness pairing, within Pearson's Hard and Soft Acids and Bases principle, constitutes a reliable predictor for the major reaction product. By taking into account an estimator for the steric effects, the correct regioisomer is predicted. Steric effects play a major role in driving the regioselectivity, as was corroborated by energy decomposition analysis of the transition states.
Sprache
Englisch
Identifikatoren
ISSN: 1089-5639
eISSN: 1520-5215
DOI: 10.1021/acs.jpca.2c06472
Titel-ID: cdi_proquest_miscellaneous_2764443801
Format
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