title: Electrostatic interactions between substituents as regioselectivity control elements in Diels-Alder cycloadditions. A DFT study of cycloadditions of 1-methoxy-4-trimethylsiloxy dienes with acrylonitrile.
abstract: The regioselectivities of Diels-Alder reactions of 1-methoxy-4-trimethylsiloxy-1,3-butadiene and the corresponding o-xylylene with acrylonitrile were explored with density functional theory. The transition state of the reaction of the diene with acrylonitrile was studied in both the gas phase and in a low dielectric (epsilon = 2.247) solvent. The regioselectivities of these reactions are predicted to be controlled by the direct electrostatic interactions between the diene and dienophile substituents. The electron-donating capacities of methoxy and trimethylsiloxy substituents are shown to be very similar and to not contribute to regioselectivity control. A prediction is made that the cycloadditions of the o-xylylene will be unselective, while 1-methoxy-4-trimethylsiloxy-1,3-butadiene will give a small preference ( approximately 5:1) in favor of the proximal methoxy and cyano groups. The thermochromic behavior of trans-disubstituted disiloxy benzocyclobutene was also explored.
authors.affiliation: Department of Chemistry and Biochemistry, University of California, Los Angeles, 405 Hilgard Ave., Los Angeles, California 90095-1569, USA.
authors.forename: Gregori
authors.initials: G
authors.lastname: Ujaque
authors.forename: Joseph E
authors.initials: JE
authors.lastname: Norton
authors.forename: K N
authors.initials: KN
authors.lastname: Houk
mesh_terms: D000181:Acrylonitrile / Q000737:chemistry*; D000466:Alkadienes / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D055672:Static Electricity; D013237:Stereoisomerism
chemical_list: D000466:Alkadienes; D000181:Acrylonitrile