Transformation of Carbon Resources’’ from the Ministry of
Education, Culture, Sports, Science and Technology, Japan.
Y. T. thanks the Japan Society for the Promotion of Science
for Young Scientists for Research Fellowships.
Notes and references
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Fig.
1 Plausible mechanism for the Diels–Alder reaction of
a-substituted a,b-unsaturated aldehydes.
4 K. A. Ahrendt, C. J. Borths and D. W. C. MacMillan, J. Am.
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2 Possible transition-state model for the asymmetric
Diels–Alder reaction of a-substituted a,b-unsaturated aldehydes.
The observed stereochemistry in the asymmetric reaction
using (R)-3d could be explained by a possible transition state
model shown in Fig. 2. In this model, a 3,5-di-tert-butylphenyl
group of (R)-3d effectively blocks one face of s-cis-aldimine,
while leaving the other face open for approach of cyclo-
pentadiene in accordance with the experimental results. In
the case of methacrolein, due to the small size of the methyl
group, the discrimination of s-cis- and s-trans-aldimines with
the 3,5-di-tert-butylphenyl group might be difficult, thereby
inducing the moderate enantioselectivity (Table 3, entry 1).
In summary, the new primary amine catalyst 3d has been deve-
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a,b-unsaturated aldehydes. The reaction afforded the desired
cycloadducts having one all-carbon quaternary stereocenter in
good yield with good to high stereoselectivity.
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This work was partially supported by a Grant-in-Aid for
Scientific Research on Priority Areas ‘‘Advanced Molecular
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