Synthesis and stereochemistry of ficisterol and norficisterol: biosynthetic implications
- 1 January 1987
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Journal of the Chemical Society, Perkin Transactions 1
- No. 6,p. 1291-1305
- https://doi.org/10.1039/p19870001291
Abstract
All four possible C-23 and C-24 stereoisomers of ficisterol and norficisterol were synthesized via Ireland's ester enolate Claisen rearrangement. The stereochemistry of each isomer was determined by a combination of stereochemical deductions derived from the Claisen mechanism, and chemical correlations with known standards. The resulting stereostructures (1a) and (2a) are consistent with the hypothesis that dihydrocalysterol (3) and (23R,24R)-methylenecholesterol (42) are the respective biosynthetic precursors of ficisterol and norficisterol, thus supporting a novel mechanism for 27-norergostane biosynthesis. In the course of the stereochemically significant synthesis, 23,24-dimethyl-22-dehydrocholesterol (37)—the presumed biosynthetic precursor of gorgosterol (41)—was prepared by a route that lends itself readily to the synthesis of isotopically labelled analogues.This publication has 9 references indexed in Scilit:
- Synthesis and stereochemistry of 23,24-dihydrocalysterol: implications for marine sterols of a unified biosynthetic scheme involving protonated cyclopropanesJournal of the Chemical Society, Perkin Transactions 1, 1987
- The crystal structure of 3β-hydroxy-4α,23R,24R-trimethyl-5α-cholestane (23R,24R-5α-dinostanol) from dinoflagellates1Steroids, 1986
- Stereochemical effects in cyclopropane ring openings: synthesis and isomerization of petrosterol and all three of its trans cyclopropane diastereomersJournal of the American Chemical Society, 1984
- Sterol patterns of cultured zooxanthellae isolated from marine invertebrates: Synthesis of gorgosterol and 23-desmethylgorgosterol by aposymbiotic algaeProceedings of the National Academy of Sciences, 1982
- Dinoflagellate sterols—3: sterol composition of the dinoflagellate Gonyaulax monilataComparative Biochemistry and Physiology Part B: Comparative Biochemistry, 1981
- Sterols with unusual nuclear unsaturation from three cultured marine dinoflagellatesPhytochemistry, 1981
- Stereospecific synthesis of the side chain of the steroidal plant sex hormone oogoniolThe Journal of Organic Chemistry, 1979
- Minor and trace sterols in marine invertebrates. 8. Isolation, structure elucidation, and partial synthesis of two novel sterols - stelliferasterol and isostelliferasterolJournal of the American Chemical Society, 1978
- Calciferol and its relatives. Part 20. A synthesis of Windaus and Grundmann's C19 ketoneJournal of the Chemical Society, Perkin Transactions 1, 1977