title: Dichlorocarbene addition to cyclopropenes: a computational study.
abstract: Reaction paths for addition of dichlorocarbene to 1,2-disubstituted cyclopropenes were calculated using hybrid density functional theory (B3LYP/6-31G) in the gas phase and in the presence of a continuum solvation model corresponding to acetonitrile. In both the gas phase and acetonitrile, :CCl2-cyclopropene addition follows an asymmetric, non-least-motion approach. Barriers to addition range from 0 to 2 kcal/mol. The reactions proceed in concerted fashion in both the gas phase and solution to yield 1,3-dienes or bicyclobutanes. The reaction pathway on this complex potential energy surface of this reaction appears to bifurcate, and the product distribution is believed to be controlled by reaction dynamics. At the present level of theory, there appears to be no minimum on the potential energy surface corresponding to a dipolar intermediate.
authors.affiliation: Department of Chemistry, Barnard College, 3009 Broadway, New York, New York 10027, USA. dmerrer@barnard.edu
authors.forename: Dina C
authors.initials: DC
authors.lastname: Merrer
authors.forename: Paul R
authors.initials: PR
authors.lastname: Rablen
mesh_terms: D003198:Computer Simulation; D003521:Cyclopropanes / Q000138:chemical synthesis* / Q000737:chemistry; D006843:Hydrocarbons, Chlorinated / Q000737:chemistry*; D008956:Models, Chemical; D015394:Molecular Structure
chemical_list: D003521:Cyclopropanes; D006843:Hydrocarbons, Chlorinated; C021985:cyclopropene; C004260:dichlorocarbene