Total syntheses of naturally occurring seimatopolide a and its enantiomer from chiral pool starting materials using a bidirectional strategy
- 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).
Author details: | Bernd SchmidtORCiDGND, Oliver Kunz, Monib H. Petersen |
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DOI: | https://doi.org/10.1021/jo302359h |
ISSN: | 0022-3263 |
Title of parent work (English): | The journal of organic chemistry |
Publisher: | American Chemical Society |
Place of publishing: | Washington |
Publication type: | Article |
Language: | English |
Year of first publication: | 2012 |
Publication year: | 2012 |
Release date: | 2017/03/26 |
Volume: | 77 |
Issue: | 23 |
Number of pages: | 10 |
First page: | 10897 |
Last Page: | 10906 |
Funding institution: | Deutsche Forschungsgemeinschaft (DFG) [Schm1095/6-2] |
Organizational units: | Mathematisch-Naturwissenschaftliche Fakultät / Institut für Chemie |
Peer review: | Referiert |