Facile entry to the tetracyclic 5-7-6-3 tigliane ring system.
[figure: see text] A tandem anionic 5-exo-dig cyclization/Claisen rearrangement sequence was used to effect a facile, "one-pot" conversion of an appropriately substituted 4-alkyn-1-ol to the tetracyclic carbon core structure of phorbol. The synthesis was conducted using readily available nonracemic starting materials to provide the target structure as a single enantiomer in high chemical yield.
Ovaska
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Department of Chemistry, Connecticut College, 270 Mohegan Avenue, New London, Connecticut 06320, USA. tvova@conncoll.edu
Reisman
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Flynn
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MA
D000480:Alkynes / Q000737:chemistry; D002384:Catalysis; D003500:Cyclization; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D010704:Phorbols / Q000737:chemistry; D011083:Polycyclic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D013237:Stereoisomerism; D013329:Structure-Activity Relationship; D014753:Vinyl Compounds / Q000737:chemistry
D000480:Alkynes; D010704:Phorbols; D011083:Polycyclic Compounds; D014753:Vinyl Compounds