Science, Vol 231, Issue 4742, 1108-1117
Copyright © 1986 by American Association for the Advancement of Science
Theory and modeling of stereoselective organic reactions
KN Houk,
MN Paddon-Row,
NG Rondan,
YD Wu,
FK Brown,
DC Spellmeyer,
JT Metz,
Y Li,
and
RJ Loncharich
Theoretical investigations of the transition structures of additions and cycloadditions reveal details about the geometries of bond-forming processes that are not directly accessible by experiment. The conformational analysis of transition states has been developed from theoretical generalizations about the preferred angle of attack by reagents on multiple bonds and predictions of conformations with respect to partially formed bonds. Qualitative rules for the prediction of the stereochemistries of organic reactions have been devised, and semi-empirical computational models have also been developed to predict the stereoselectivities of reactions of large organic molecules, such as nucleophilic additions to carbonyls, electrophilic hydroborations and cycloadditions, and intramolecular radical additions and cycloadditions.
