1. Fachbereich Chemie, Philipps‐Universit?t Marburg, Hans‐Meerwein‐Strasse, 35043 Marburg (Germany);2. Present address: Departamento de Química Orgánica, Facultad de Química, Universidad Complutense, 28040 Madrid (Spain);3. Massespektrometrilaboratoriet og Senter for teoretisk og beregningsbasert kjemi (CTCC), Kjemisk institutt Universitetet i Oslo, Postboks 1033 Blindern, 0315 Oslo (Norway), Fax: (+47)?22 8554 41
Abstract:
Myths of steric hindrance : In contrast with current opinion, energy decomposition analysis shows that the presence of bulky substituents at carbon leads to the release of steric repulsion in the transition state shown in the graphic. It is rather the weakening of the electrostatic attraction, and in particular the loss of attractive orbital interactions, that are responsible for the activation barrier.