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dienophile). For E approach, where the smallest H is on the bottom side of the diene, the bulky R group
is in a gauche disposition with respect to the C2–C3 double bond and also in the face of the approaching
dienophile. This could be the origin of the formation of minor compounds 5. The matched pair in this like
approach arose from the evolution of (S)-2a–c or (R)-2d–f dienes. According to previous results, π-facial
diastereoselectivity of cycloadditions with sulfinylquinones strongly increases with low temperatures.
Thus, the moderate reactivity of dienes 2, which reacted at rt or 40°C could justify the formation of a
minor amount (9–16%) of the corresponding enantiomers of 4 and 5 (see Table 1).
In summary, the enantioselective reaction of acyclic dienes bearing an allylic stereogenic center
with (S)-2-p-tolylsulfinyl-1,4-naphthoquinone is reported as a useful synthetic approach to chiral 1,4-
dihydro-9,10-anthraquinone derivatives which takes advantage of the kinetic resolution of racemic dienes
observed in these processes. The extension of this methodology to the synthesis of other quinones of
interest is under way.
Acknowledgements
We thank Dirección General de Investigación Científica y Técnica (Grant PB95-0174) for financial
support. CDV thanks FAPESP-Fundação de Amparo à Pesquisa do Estado de São Paulo for a post-
doctoral fellowship.
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