Chemistry of hexafluorobicyclo[1.1.0]butane: a computational study.
Despite its very weak central C-C bond, the yet-unknown hexafluorobicyclobutane is predicted to be quite robust. Unlike the parent hydrocarbon, which undergoes thermal rearrangement to butadiene, the perfluoro compound will yield hexafluorocyclobutene upon heating. The fluorobicyclobutane will react under mild conditions with a variety of reagents, in particular with certain alkenes in a new type of concerted transformation. This "fluorohomoene" reaction is shown to be a pseudopericyclic process, as is condensation of the bicyclobutane with water. Whereas the carbene 3-butenylidene rearranges primarily to butadiene, its perfluoro counterpart is predicted to be an efficient precursor for hexafluorobicyclobutane.
Lemal
David M
DM
Department of Chemistry, Dartmouth College, Hanover, New Hampshire 03755, USA. david.m.lemal@dartmouth.edu
D000438:Alcohols / Q000737:chemistry; D000475:Alkenes / Q000737:chemistry; D001643:Bridged Bicyclo Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D003198:Computer Simulation; D006845:Hydrocarbons, Fluorinated / Q000138:chemical synthesis / Q000737:chemistry*; D015394:Molecular Structure; D013816:Thermodynamics
D000438:Alcohols; D000475:Alkenes; D001643:Bridged Bicyclo Compounds; D006845:Hydrocarbons, Fluorinated; C554649:hexafluorobicyclo(1.1.0)butane