206191-85-7Relevant articles and documents
Studies directed to the synthesis of the antifungal antibiotic aleurodiscal. Enantioselective construction of an advanced β-D-xyloside congener
Paquette, Leo A.,Heidelbaugh, Todd M.
, p. 495 - 508 (1998)
The first synthesis of a highly functionalized congener of aleurodiscal is reported. An enantiocontrolled route to tricyclic ketone 8 was first developed by taking advantage of regiodirected tandem methylation and vinylation of a phenylsulfanyl precursor, as 23 → 24 → 8. These experiments formed the basis for the coupling of 8 to 30, in turn prepared from (4S)-(- )-tert-butyldimethylsiloxycyclopentenone, prior to oxy-anionic Cope rearrangement. Phenylselenenylation of the enolate ion generated in this manner ultimately led to a pair of dienone isomers, whose distinctively different chemistries were made apparent at several levels. Notable features of the overall approach include the introduction of stereogenic centers positioned remotely from each other across a medium-sized ring and stereoselective bond construction via a boatlike transition state following efficient conjoining of the two key segments.