Unusual transannular cyclization products of sarcophytoxide, a 14-membered marine cembranoid: anomalous stereochemistry of epoxide-ketone rearrangement.
[reaction: see text] Treatment of sarcophytoxide with trimethylsilyl trifluoromethanesulfonate afforded an aromatic ketone as an unusual cyclization product. The modified Mosher's method and X-ray analysis performed on the aromatic ketone revealed that it is a 4:1 mixture of 8(R)- and 8(S)-enantiomers. It also suggested that the precursor ketone has 8(R)-configuration, which is contradictory to that expected from the ordinary epoxide-ketone rearrangement.
Nii
Keiji
K
Institute of Health Biosciences, The University of Tokushima Graduate School, Japan.
Tagami
Keiko
K
Matsuoka
Keisuke
K
Munakata
Tatsuo
T
Ooi
Takashi
T
Kusumi
Takenori
T
D015107:4-Butyrolactone / Q000031:analogs & derivatives / Q000494:pharmacology; D000818:Animals; D037421:Anthozoa / Q000737:chemistry; D018360:Crystallography, X-Ray; D003500:Cyclization; D004224:Diterpenes / Q000138:chemical synthesis* / Q000737:chemistry* / Q000494:pharmacology; D004852:Epoxy Compounds / Q000737:chemistry*; D006801:Humans; D007659:Ketones / Q000737:chemistry*; D008386:Marine Biology; D008968:Molecular Conformation; D015394:Molecular Structure; D013237:Stereoisomerism
D004224:Diterpenes; D004852:Epoxy Compounds; D007659:Ketones; C518942:sarcophytoxide; C014804:sarcophine; D015107:4-Butyrolactone