2786
J.P.M. Nunes et al. / Tetrahedron 67 (2011) 2779e2787
Our milder conditions for this rearrangement allowed for tele-
Supplementary data
scoping this transformation through the dynamic kinetic resolution
to afford enantiomerically enriched acylated cyclopentenone (ꢀ)-5.
Thus we developed a one-pot, sequential method whereupon the
rearrangement is carried out first, followed by a lipase-catalyzed
acylation. AK Amano 20 was the best enzyme at elevated temper-
ature using a polar solvent mixture and silica gel. Under these
conditions the target cyclopentenone (ꢀ)-5 could be isolated in
high yield and excellent enantiomeric purity. We applied this
methodology to other pyranone analogues albeit with slightly
poorer yields and optical purities. To the best of our knowledge this
is the first case of a dynamic kinetic resolution as an asymmetric
synthesis strategy for enantiomerically enriched trans-dioxy-
genated cyclopentenone.
Spectral data and experimental procedures for all new com-
pounds. Representative chromatograms of reaction samples and of
racemic and enantiomerically enriched compounds. Spectral data
for deuteration and mass spectrometry studies. Additional table
and graphs for rearrangement and resolution studies. Computa-
tional details and associated reference list. Supplementary data
associated with this article can be found in online version at
InChIKeys of the most important compounds described in this
article.
References and notes
4. Experimental
4.1. General
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Acknowledgements
The authors are grateful to Dr. Anne Mortimer and Dr. Richard
~
Fitzmaurice for helpful comments on the manuscript, to Fundac¸ ao
ˇ
para a Ciencia e a Tecnologia, (POCI 2010) and FEDER for financial
support (Ref. SFRH/BD/31678/2006, PTDC/QUI/73061/2006 and
PTDC/QUI-QUI/099389/2008), the Portuguese Nuclear Magnetic
ꢀ
Resonance Network (Instituto Superior Tecnico) for NMR spectra,
ˇ
Rede Nacional de Espectrometria de Massa (Faculdade de Ciencias
da Universidade de Lisboa) for FT-ICR mass spectra, Unidade de
Espectrometría de Masas (Universidad de Santiago de Compostela),
University College London for EI and FAB mass spectra and Amano
for gift of the enzymes.
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