Jm. Hawkins et al., ASYMMETRIC LEWIS ACID-DIENOPHILE COMPLEXATION - SECONDARY ATTRACTION VERSUS CATALYST POLARIZABILITY, Journal of the American Chemical Society, 116(5), 1994, pp. 1657-1660
A series of five X-ray crystal structures of chiral Lewis acid-dienoph
ile complexes support a two-point-binding chiral recognition mechanism
for these asymmetric Diels-Alder catalysts. As the arene moieties of
the alkyldichloroborane Lewis acids are made more polarizable through
the progression of phenyl to 3,5-dimethylphenyl to 3,5-dichlorophenyl
to 3,5-dibromophenyl to naphthyl, the polar ester group of the boron-b
ound methyl crotonate is drawn in toward the arene of the catalyst due
to an enhanced dipole-induced-dipole attraction. The catalyst with th
e most polarizable arene (1-naphthyl) gives higher enantioselectivity
(up to 99.5% ee) in Diels-Alder reactions than the catalyst with the l
east polarizable arene (phenyl), demonstrating that this effect transl
ates to the transition state.