TY - JOUR
T1 - A chemoenzymatic synthesis of the cis-decalin core associated with the novel anti-mitotic agent phomopsidin
T2 - Some observations concerning a high-pressure-promoted diels-alder cycloaddition reaction of (1S,2R)-3-methyl-cis-1,2-dihydrocatechol and the anionic oxy-cope rearrangement of compounds derived from the adduct
AU - Banwell, Martin G.
AU - Edwards, Alison J.
AU - McLeod, Malcolm D.
AU - Stewart, Scott G.
PY - 2004
Y1 - 2004
N2 - The enantiomerically pure and enzymatically derived cis-1,2-dihydrocatechol 2 engages in a diastereofacially selective Diels-Alder cycloaddition reaction with commercially available lactone 3 at 19 kbar to afford adduct 4, which is readily elaborated to the diene-ol 13. Treatment of this last compound with KH/18 [crown]-6 resulted in successive anionic oxy-Cope and 1,2-Wittig rearrangements to afford acyloin 14 embodying the cis-decalin core associated with the natural product phomopsidin (1). Compound 16 also engages in an anionic oxy-Cope rearrangement reaction to give, depending on the molar equivalents of base used, either the cis-decalin 17 or the hexahydroindene 18. The structure of compound 18 has been established by single-crystal X-ray diffraction analysis.
AB - The enantiomerically pure and enzymatically derived cis-1,2-dihydrocatechol 2 engages in a diastereofacially selective Diels-Alder cycloaddition reaction with commercially available lactone 3 at 19 kbar to afford adduct 4, which is readily elaborated to the diene-ol 13. Treatment of this last compound with KH/18 [crown]-6 resulted in successive anionic oxy-Cope and 1,2-Wittig rearrangements to afford acyloin 14 embodying the cis-decalin core associated with the natural product phomopsidin (1). Compound 16 also engages in an anionic oxy-Cope rearrangement reaction to give, depending on the molar equivalents of base used, either the cis-decalin 17 or the hexahydroindene 18. The structure of compound 18 has been established by single-crystal X-ray diffraction analysis.
UR - http://www.scopus.com/inward/record.url?scp=3242735973&partnerID=8YFLogxK
U2 - 10.1071/CH04036
DO - 10.1071/CH04036
M3 - Article
SN - 0004-9425
VL - 57
SP - 641
EP - 644
JO - Australian Journal of Chemistry
JF - Australian Journal of Chemistry
IS - 7
ER -