Abstract
Total synyhesis of polygalolide A, a secondary metabolite isolated from a Chinese medicinal plant, was achieved. In order to construct an oxabicyclo [3.2.1] core skeleton, we have developed an intramolecular Ferrier-type C-glycosylation of a glucal modified with siloxyfuran as an internal nucleophile. Although the conditions found in the model experiments did not undergo the C-glycosylation, further examination led us to find that combination of TMSOTf and 2,4,6-collidine was the best condition, giving oxabicyclo [3.2.l]octene with correct quaternary stereogenic centers in high yield. The successful production of the single diastereomer indicated that the siloxy group at the C-3 position played a crucial role for the stereocontrol. After transformation into tetracyclic intermediate, a phenolic moiety was finally introduced by Mukaiyama aldol reaction to furnish polygalolide A.
Original language | English |
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Pages (from-to) | 607-615 |
Number of pages | 9 |
Journal | Yuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry |
Volume | 73 |
Issue number | 6 |
DOIs | |
Publication status | Published - 2015 Jun |
Externally published | Yes |
Keywords
- Asymmetric synthesis
- C-glycosylation
- Glucal
- Natural products
- Polygalolide
- Siloxyfuran
- Total synthesis
ASJC Scopus subject areas
- Organic Chemistry