o-Fluoranil: stereochemistry and mechanism of its Diels-Alder reactions.
In the absence of significant steric effects, Diels-Alder reactions of the title quinone generally take place with preservation of configuration, and are therefore probably concerted. However, hybrid density functional calculations indicate that often these reactions are highly asynchronous. Steric hindrance can result in reaction at quinone oxygen instead of carbon. Preference for endo over exo cycloaddition is observed, and is reinforced by a repulsive secondary orbital interaction in exo transition states.
Lemal
David M
DM
Department of Chemistry, Dartmouth College, Hanover, New Hampshire 03755, USA. david.m.lemal@dartmouth.edu
Sang
Dayong
D
Ramanathan
Sudharsanam
S