Understanding the sigmatropic shifts of cyclopenta-2,4-dien-1-yltrimethylsilane in its Diels–Alder addition

Investigation on the dynamic processes of 1-(C5H5)Si(Me)3 in its Diels–Alder addition showed that Si(Me)3 migration is the dominant factor and hydrogen shifts are negligible.

Effects of electrostatic drag on the velocity of hydrogen migration – pre- and post-transition state enthalpy/entropy compensation

Ab initio molecular dynamics calculations were used to explore the underlying factors that modulate the velocity of hydrogen migration for 1,2 hydrogen shifts in carbocations in which different groups interact noncovalently with the migrating hydrogen.

Dynamic correlation diagrams for sigmatropic reactions based on orbital phase conservation theory

For sigmatropic reactions, such as [1,3] and [1,5] hydrogen shifts, the Cope and Claisen rearrangements, and the Berson–Nelson rearrangement, no correlation diagrams consistent with the classical electronic formulas have been reported. Here, we report dynamic correlation diagrams for these sigmatropic reactions based on orbital phase conservation theory. The diagrams are consistent with both the selection rules of sigmatropic reactions proposed by Woodward and Hoffmann and classical electronic formulas.