[Studies on the biosynthesis of sterol side chain in higher plants].
Campesterol (3) and dihydrobrassicasterol (4), typical C28-sterols in higher plants, are biosynthesized from a steroidal 24-ene precursor (desmosterol 1) via 24-methylenecholesterol (2) and 24-methyldesmosterol (5). A typical plant C29-sterol, sitosterol (6), is produced from 24-methylenecholesterol via isofucosterol (7) and 24-ethyldesmosterol (8). The biosynthetic mechanism, focussing stereochemical features, of these side-chain transformations has been studied in detail by feeding regio- and stereoselectively 13C- or 2H-labeled steroidal substrates to cell cultures of higher plants such as Oryza sativa, Catharanthus roseus and Morus alba. These studies allowed to correlate the metabolic origin of C-26 and C-27 of the intermediate sterols. It has been established that the 1st methylation leading to 24-methylenecholesterol from desmosterol involves a Re-face hydrogen migration from C-24 to C-25 based on unambiguous assignment of the isopropyl pro-R-Me and pro-S-Me of 24-methylenecholesterol. The 2nd methylation leading to isofucosterol was revealed to proceed in a trans-mechanism in which addition of the methyl group and elimination of the C-28 hydrogen occur on opposite faces of the original delta 24(28) plane. The double bond isomerization from delta 24(28) to delta 24(25) was found to proceed in a syn-SE2' mechanism with the pro-S-methyl group of isofucosterol becoming the (E)-methyl of 24-ethyldesmosterol. Finally, feeding studies of [E-Me-13C]- and [Z-Me-13C]-24-methyldesmosterols established that an anti-mode of hydrogen addition is operating in the conversion of 24-methyldesmosterol to campesterol and dihydrobrassicasterol. Similar studies established that 24-ethyldesmosterol is converted to sitosterol in an anti-mode of hydrogen addition. In addition, the mechanism of sterol side-chain formation in hairy roots of Ajuga reptans var. atropurpurea is briefly described.
Fujimoto
Y
Y
Department of Chemistry and Materials Science, Tokyo Institute of Technology, Japan.
Morisaki
M
M
Ikekawa
N
N
D003897:Desmosterol / Q000378:metabolism; D010084:Oxidation-Reduction; D010840:Phytosterols / Q000096:biosynthesis*; D010944:Plants / Q000378:metabolism*; D013237:Stereoisomerism
D010840:Phytosterols; D003897:Desmosterol