Total Synthesis of the Rubrolone Aglycon
Journal of the American Chemical Society2000Vol. 122(49), pp. 12169–12173
Citations Over TimeTop 23% of 2000 papers
Abstract
A total synthesis of the rubrolone aglycon is detailed and is based on two key Diels−Alder reactions. The AB ring system incorporating a tetrasubstituted pyridine was assembled, enlisting the rare 4π participation of an O-alkyl α,β-unsaturated oxime in an intramolecular [4 + 2] cycloaddition reaction (70%). The C-ring oxygenated tropolone was introduced through a room-temperature, exo selective [4 + 2] cycloaddition of a cyclopropenone ketal (97%) followed by in situ generation of a norcaradiene and room-temperature electrocyclic rearrangement to a cycloheptatrienone ketal appropriately substituted for hydrolysis directly to a 2,4-dihydroxycycloheptatrienone.
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