On the mechanism of catalytic enantioselective hetero-Diels-Alder reactions of carbonyl compounds catalyzed by chiral aluminum complexes - a concerted, step-wise or Mukaiyama-aldol pathway
M. Roberson et al., On the mechanism of catalytic enantioselective hetero-Diels-Alder reactions of carbonyl compounds catalyzed by chiral aluminum complexes - a concerted, step-wise or Mukaiyama-aldol pathway, TETRAHEDRON, 57(5), 2001, pp. 907-913
The mechanism for the hetero-Diels-Alder reaction of benzaldehyde with Dani
shefsky's diene catalyzed by various types of achiral and chiral aluminum c
omplexes has been studied from a theoretical point of view using semi-empir
ical and ab initio calculations. The uncatalyzed reaction proceeds as a con
certed reaction with an unsymmetrical transition state. The catalytic react
ion has been studied using first (MeO)(2)AlMe, followed by (S)-BINOL-AlMe a
s the catalysts, and the transition states and intermediates have been calc
ulated for different reaction paths. The catalyst activates benzaldehyde ma
king the carbon atom in the carbonyl, functionality more electrophilic. Att
empts to calculate a concerted reaction path failed. However, a two-step pr
ocess, the first step being a nucleophilic attack of the activated diene to
the carbonyl carbon atom, with a transition-state energy of up to 13 kcal
mol(-1), depending on the catalyst and calculation method used, was found t
o take place leading to an aldol-like local energy-minimum intermediate. Th
e second step, the ring-closure, which has a significantly lower transit-io
n-state energy leads to the hetero-Diels-Alder adduct. The mechanistic aspe
cts of the catalytic hetero-Diels-Alder reaction is discussed on the basis
of the calculations. (C) 2001 Elsevier Science Ltd. All rights reserved.