NDLI: Predicting Reactivity and Stereoselectivity in the Nazarov Reaction: A Combined Computational and Experimental Study

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Predicting Reactivity and Stereoselectivity in the Nazarov Reaction: A Combined Computational and Experimental Study

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Occhiato, Ernesto G. Recanatini, Maurizio Cavalli, Andrea Prandi, Cristina Pacetti, Alessandro Scarpi, Dina
Description	Author Affiliation: Cavalli A ( Dipartimento di Scienze Farmaceutiche, Alma Mater Studiorum-Università di Bologna, Via Belmeloro 6, 40126 Bologna, Italy.)
Abstract	The Nazarov reaction of pentadienyl cations generated by protonation of either dienones or alkoxytrienes has been examined in detail both experimentally and by DFT calculations. In particular, calculations at the B3LYP/6-311G level of theory accurately predicted, and accounted for, the outcome of the Brønsted acid catalyzed electrocyclization of 4π-electron systems in which one of the double bonds involved in the process was embedded in N- and S-heterocyclic rings. Calculations showed that both heteroatoms are capable of accelerating the ring closure by stabilizing the partial positive charge which develops at C-6 (C-2) in the transition state, with S-heterocyclic derivatives being more reactive than the corresponding N-containing compounds. In general, pentadienyl cations generated by protonation of alkoxytrienes were expected to react faster than those obtained by protonation of the corresponding dienones, as the latter were stabilized by a hydrogen bond. The presence of a substituent on the heterocyclic ring significantly affects the stereoselectivity (torquoselectivity) only in the case of the N-heterocyclic derivatives, in which a 2-alkyl group is axially oriented, providing the cis-2,5-disubstituted isomer only. Instead, with substituted S-heterocyclic compounds, the anticipated torquoselectivity was very low and, in fact, a 3:1 diastereomeric mixture between the trans and cis products was experimentally found after ring closure. For this study, the synthesis of the appropriate N- and S-containing dienones and alkoxytrienes was realized to evaluate the predictivity power of the DFT computations, which was very good in all of the cases examined, both in terms of reactivity and stereoselectivity. The consistency observed between computational and experimental results, therefore, shows the usefulness of DFT calculations at the B3LYP/6-311G level of theory as a robust instrument for the prediction of reactivity and stereoselectivity in the Nazarov electrocyclic reaction.
ISSN	09476539
e-ISSN	15213765
Journal	Chemistry - A European Journal
Issue Number	30
Volume Number	14
Language	English
Publisher	Wiley-VCH;ChemPubSoc Europe
Publisher Date	2008-01-01
Publisher Place	Germany
Access Restriction	Open
Subject Keyword	Heterocyclic Compounds Chemistry Quantum Theory Alcohols Electrons Polyenes Stereoisomerism Substrate Specificity Thermodynamics Research Support, Non-U.S. Gov't
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry Catalysis

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