The rearrangement of some cyclopentanone-aryloximes: synthesis of (±)-aplysin, (±)-filiformin and of their debromo analogues. |
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Authors: | J. Yves Laronze Rachida El Boukili Dominique Patigny Seloua Dridi Dominique Cartier Lean L vy |
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Affiliation: | Laboratoire de Transformations et Synthèse de Substances Naturelles, associé au CNRS, Université de Reims-Champagne-Ardenne, Faculté de Pharmacie, 51, rue Cognacq-Jay, 51096 Reims Cédex, France |
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Abstract: | Upon acid catalyzed rearrangement after Sheradsky, the aryloximes A gave the tricyclic aminals C, which suffered hydrolysis to lactols E. The unique alcohol 29 was then prepared through a highly stereoselective equilibration-reductive alkylation of the epimeric mixture of lactols 22a,b. Two routes, one of which was stereospecific, allowed cyclization of 29 to (±)-aplysin 34. The yield was 2.5 % from oximes 2a,b. The isomeric epi-aplysin 35 and filiformin 36 were also obtained from 29. The debromo analogues 37,38 and 39 and their trideutero derivatives 41,42 and 43 were synthesized along similar line and allowed unequivocal structure elucidation by NMR spectroscopy. |
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Keywords: | Sesquiterpene aplysin filiformin rearrangement of aryloximes cyclopentanodihydrobenzofuranes diastereoselective equilibration-alkylation of a lactol. |
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