Multiple Transition States
In organic synthesis, bimolecular reactions offer a large variety of
possible transition states which often differ only by configurational
changes. The corresponding energy differences are subtle, but relying on the
fact that only relative energies are
important in ee
(enantiomeric excess) calculations, systematic errors
are expected to cancel out.
Recently, we have published a systematic approach to the simulation of
multiple-transition-state reactions.
Recent papers:
Determination of the origin of stereoselectivity
in multiple-transition-state reactions using DFT calculations: Enantioselective synthesis of homoallylic
alcohols from aliphatic methyl ketones via an
auxiliary-mediated allylation,
L. F. Tietze, T. Kinzel and S. Schmatz,
J. Am. Chem. Soc. 130, 4386 (2008).
Origin of syn/anti diastereoselectivity
in aldehyde and ketone crotylation reactions: A combined theoretical and
experimental study,
L. F. Tietze, T. Kinzel and S. Schmatz,
J. Am. Chem. Soc. 128, 11483 (2006).