TOTAL SYNTHESIS OF (+ -)-TREMULENOLIDE-A AND (+/-)-TREMULENEDIOL-A VIA A STEREOSELECTIVE CYCLOPROPANATION/COPE REARRANGEMENT ANNULATION STRATEGY/

Authors
DAVIES HML DOAN BD
Citation
Hml. Davies et Bd. Doan, TOTAL SYNTHESIS OF (+ -)-TREMULENOLIDE-A AND (+/-)-TREMULENEDIOL-A VIA A STEREOSELECTIVE CYCLOPROPANATION/COPE REARRANGEMENT ANNULATION STRATEGY/, Journal of organic chemistry, 63(3), 1998, pp. 657-660
Citations number
22
Categorie Soggetti
Chemistry Inorganic & Nuclear
Journal title
Journal of organic chemistry → ACNP
ISSN journal
00223263
Volume
63
Issue
3
Year of publication
1998
Pages
657 - 660
Database
ISI
SICI code
0022-3263(1998)63:3<657:TSO(-A>2.0.ZU;2-8
Abstract
Short total syntheses of (+/-)-tremulenolide A (1) and (+/-)-tremulene diol A (2) are described. The critical step is a dirhodium tetracarbox ylate-catalyzed tandem cyclopropanation/Cope rearrangement between the vinyldiazoacetate 4 and the 2(Z),4(E)-hexadiene 5. This step results in full control of the relative stereochemistry at the three stereogen ic centers that exist in the natural products. Due to problems with al kene face selectivity, the approach was not amenable to an efficient a symmetric synthesis of 1 and 2.