Total synthesis of the reputed structure of alcyonin and reassignment of its structure.
Introduction of the C4 hydroxyl group by an epoxy ester rearrangement is a pivotal step in the first total synthesis of the purported structure of alcyonin. As the spectral data for diol acetate 3 do not match those reported for alcyonin, the structure of this marine diterpene must be revised. Reexamination of NMR spectra, MS data, and chemical transformations of natural alcyonin suggests that the structure of this marine metabolite is allylic peroxide 15.[structure: see text]
Corminboeuf
Olivier
O
Department of Chemistry, 516 Rowland Hall, University of California, Irvine, CA 92697-2025, USA.
Overman
Larry E
LE
Pennington
Lewis D
LD
D000107:Acetylation; D000498:Allyl Compounds / Q000737:chemistry; D037421:Anthozoa / Q000737:chemistry; D002244:Carbon / Q000737:chemistry; D003500:Cyclization; D004224:Diterpenes / Q000138:chemical synthesis* / Q000737:chemistry*; D004852:Epoxy Compounds / Q000737:chemistry; D004952:Esters / Q000737:chemistry; D004987:Ethers / Q000138:chemical synthesis*; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D015394:Molecular Structure; D010545:Peroxides / Q000737:chemistry
D000498:Allyl Compounds; D004224:Diterpenes; D004852:Epoxy Compounds; D004952:Esters; D004987:Ethers; D010545:Peroxides; C476170:alcyonin; D002244:Carbon