Halogenation Effects in Intramolecular Furan Diels-Alder Reactions: Broad Scope Synthetic and Computational Studies
Document Type
Article
Publication Date
12-7-2013
Abstract
For the first time a comprehensive synthetic and computational study of the effect of halogen substitution on both furan and dienophile for the intramolecular Furan Diels-Alder (IMDAF) reaction has been undertaken. Contrary to our initial expectations, halogen substitution on the dienophile was found to have a significant effect, making the reactions slower and less thermodynamically favourable. However, careful choice of the site of furan halogenation could be used to overcome dienophile halogen substitution, leading to highly functionalised cycloadducts. These reactions are thought to be controlled by the interplay of three factors: positive charge stabilisation in the transition state and product, steric effects and a dipolar interaction term identified by high level calculations. Frontier orbital effects do not appear to make a major contribution in determining the viability of these reactions, which is consistent with our analysis of calculated transition state structural data.
DOI
10.1039/c3ob41616jFinal published version Open
Montclair State University Digital Commons Citation
Rae, Robert L.; Zurek, Justyna M.; Paterson, Martin J.; and Bebbington, Magnus, "Halogenation Effects in Intramolecular Furan Diels-Alder Reactions: Broad Scope Synthetic and Computational Studies" (2013). Department of Chemistry and Biochemistry Faculty Scholarship and Creative Works. 135.
https://digitalcommons.montclair.edu/chem-biochem-facpubs/135