Formal total synthesis of (-)-apicularen A via transannular conjugate addition.
The formal total synthesis of the myxobacteria metabolite (-)-apicularen A (1) is described. The key step involved a novel acid-mediated transannular conjugate addition of the C13 hydroxyl into the alpha,beta-unsaturated ketone in either of the macrolactones 5a or 5b to provide the same trans-pyranone 4. Conversion of 4 into the known apicularen intermediate diol 3 completed the formal synthesis. [reaction: see text]
Hilli
Ferdows
F
School of Chemistry, The University of Melbourne, Victoria 3010, Australia.
White
Jonathan M
JM
Rizzacasa
Mark A
MA
D000970:Antineoplastic Agents / Q000138:chemical synthesis* / Q000494:pharmacology; D019086:Bridged Bicyclo Compounds, Heterocyclic / Q000138:chemical synthesis* / Q000494:pharmacology; D002384:Catalysis; D003500:Cyclization; D007659:Ketones / Q000737:chemistry*; D007783:Lactones / Q000737:chemistry; D018942:Macrolides / Q000737:chemistry; D008958:Models, Molecular; D009231:Myxococcales / Q000378:metabolism; D011714:Pyrans / Q000737:chemistry; D013237:Stereoisomerism; D013696:Temperature
D000970:Antineoplastic Agents; D019086:Bridged Bicyclo Compounds, Heterocyclic; D007659:Ketones; D007783:Lactones; D018942:Macrolides; D011714:Pyrans; C117813:apicularen A