Total syntheses of naturally occurring seimatopolide A and its enantiomer from chiral pool starting materials using a bidirectional strategy.
J Org Chem
; 77(23): 10897-906, 2012 Dec 07.
Article
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| MEDLINE
| ID: mdl-23148441
ABSTRACT
Enantioselective total syntheses of both enantiomers of the recently isolated decanolide natural product seimatopolide A are described. The C(2)-symmetric building blocks (R,R)-hexa-1,5-diene-3,4-diol (derived from D-mannitol) and its enantiomer (derived from l-(+)-tartrate) serve as key starting materials, which are elaborated in a bidirectional way using a selective mono-cross-metathesis, regio- and stereoselective epoxidation, and regioselective reductive epoxide opening to furnish the first fragment. Both enantiomers of the second fragment, 3-hydroxypent-4-enoic acid, were conveniently obtained through a lipase-catalyzed kinetic resolution and merged with the first fragment via Shiina esterification. An E-selective ring-closing metathesis was used to access the 10-membered lactone. A comparison of the specific optical rotations of synthetic seimatopolides with those reported for the natural product suggests that the originally assigned (3R,6R,7R,9S)-configuration should be corrected to (3S,6S,7S,9R).
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Colección:
01-internacional
Base de datos:
MEDLINE
Asunto principal:
Macrólidos
Idioma:
En
Revista:
J Org Chem
Año:
2012
Tipo del documento:
Article
País de afiliación:
Alemania