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Preparation of methyl cis ‐9, cis ‐12, cis ‐15‐octadecatrienoate‐15,16‐ d 2 and methyl cis ‐9, cis ‐12, cis ‐15‐octadecatrienoate‐6,6,7,7‐ d 4
Author(s) -
Rakoff Henry
Publication year - 1988
Publication title -
lipids
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.601
H-Index - 120
eISSN - 1558-9307
pISSN - 0024-4201
DOI - 10.1007/bf02537333
Subject(s) - wittig reaction , deuterium , chemistry , bromide , methyl iodide , cis–trans isomerism , catalysis , medicinal chemistry , stereochemistry , organic chemistry , physics , quantum mechanics
Methyl cis ‐9, cis ‐12, cis ‐15‐octadecatrienoate‐15,16‐ d 2 was obtained from Wittig coupling of methyl 12‐oxo‐ cis ‐9‐dodecenoate, 18 , and 3,4‐dideutero‐ cis ‐3‐hexenyltriphenylphosphonium bromide, 16 . Compound 18 was obtained by periodic acid oxidation of methyl 12,13‐dihydroxy‐ cis ‐9‐octadecenoate, 17 , obtained from Vernonia oil. Compound 18 also was synthesized from methyl oleate as the starting material. The deuterated fragment, 16 , was prepared from 3‐hexynol and using Lindlar's catalyst and deuterium gas to introduce the deuterium atoms. Methyl cis ‐9, cis ‐12, cis ‐15‐octadecatrienoate‐6,6,7,7‐ d 4 was prepared by Wittig coupling of 3,6‐nonadienyltriphenylphosphonium iodide, 5 , with methyl 9‐oxononanoate‐6,6,7,7‐ d 4 , 11 . Deuterium atoms were introduced during the synthesis of 11 from 3‐butynol and 5‐bromopentanoic acid with deuterium gas in the presence of [Ph 3 P] 3 ‐RhCl. For the preparation of 5 , the 3,6‐nonadiynol intermediate was reduced to 3,6‐nonadienol with P‐2 Nickel and hydrogen. The final products were separated from isomers formed during the synthetic sequences by silver resin chromatography.