Tetrahydropyran formation by rearrangement of an epoxy ester: a model for the biosynthesis of marine polyether toxins.
Acid-catalyzed rearrangement of the (S)-epoxide derived from 2alpha-allyl cholestanyl acetate resulted in a 1:1 mixture of a steroidal tetrahydrofuran and a steroidal tetrahydropyran. Formation of a six-membered ring supports the hypothesis that epoxy ester-orthester-cyclic ether rearrangement may be involved in the biosynthesis of ladder-type marine polyether toxins. This reaction represents a new biomimetic preparation of medium ring cyclic ethers.
Giner
José-Luis
JL
Department of Chemistry, State University of New York-ESF, Syracuse, New York 13210, USA. jlginer@syr.edu
D000818:Animals; D003500:Cyclization; D004141:Dinoflagellida / Q000378:metabolism; D004852:Epoxy Compounds / Q000737:chemistry*; D004952:Esters; D004988:Ethers, Cyclic / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008387:Marine Toxins / Q000096:biosynthesis*; D008954:Models, Biological; D011714:Pyrans / Q000737:chemistry*; D013237:Stereoisomerism
D004852:Epoxy Compounds; D004952:Esters; D004988:Ethers, Cyclic; D008387:Marine Toxins; D011714:Pyrans