Substituent Effects on the Ring-Opening Mechanism of Lithium Bromocyclopropylidenoids to Allenes

AZİZOĞLU A., BALCI M. , Mieusset J., Brinker U. H.

JOURNAL OF ORGANIC CHEMISTRY, cilt.73, sa.21, ss.8182-8188, 2008 (SCI İndekslerine Giren Dergi) identifier identifier identifier

  • Cilt numarası: 73 Konu: 21
  • Basım Tarihi: 2008
  • Doi Numarası: 10.1021/jo8011144
  • Sayfa Sayıları: ss.8182-8188


The ring-opening reactions of lithium bromocyclopropylidenoids to allenes have been investigated computationally at the B3LYP/6-31 G(d) level of theory. Formally, two pathways can be considered: the reaction may either proceed in a concerted fashion or stepwise with the intermediacy of a free cyclopropylidene. In both cases, the loss of the bromide ion determines the kinetic of the reaction. The stability of the reactive intermediate, i.e., the carbene, is dependent on the substituent. Cyclopropylidenes bearing an electron-donating group (+M) are extremely unstable and ring-open readily to the allene. In contrast, bromocyclopropylidenoids with electron-withdrawing groups are particularly stable species. Here, a high energy barrier needs to be overcome in order to split off bromide and to generate the corresponding carbene or allene. Still, for most of the monosubstituted cyclopropylidenes investigated during this Study, the activation energy for the cyclopropylidene to allene rearrangement is lower than the energy required for parent compound (X = H) except for X = -SiH3 and -CF3.