Reactions of endo-3-diazotricyclo[3.2.1.0 2,4]oct-6-ene, a potential precursor for the generation of a neutral C8H8 molecule with a pyramidally coordinated carbon.
endo-3-Diazotricyclo[3.2.1.0(2,4)]oct-6-ene (endo-6) has already been prepared in solution. According to B3LYP/6-311+G(d,p) computations, the corresponding carbene endo-7 easily produces the highly strained neutral C8H8 compound 4 comprising a pyramidally tetracoordinated carbon which then rearranges to bridgehead alkene 15 through a cascade of rearrangements. Nonplanar diazocyclopropane structures are predicted for endo- and exo-6. Furthermore, their ring-opened isomers 27 are the first representatives of a new class of non-Kekulé compounds, the diazoallyls.
Mieusset
Jean-Luc
JL
Institut für Organische Chemie, Universität Wien, Währinger Strasse 38, A-1090 Vienna, Austria.
Brinker
Udo H
UH