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Toward new biosilicones: hydrosilylation of fish oil unsaturated fatty acid esters
Author(s) -
Delpech Fabien,
Asgatay Saadia,
Castel Annie,
Rivière Pierre,
RivièreBaudet Monique,
AminAlami Amal,
Manriquez Juan
Publication year - 2001
Publication title -
applied organometallic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.53
H-Index - 71
eISSN - 1099-0739
pISSN - 0268-2605
DOI - 10.1002/aoc.198
Subject(s) - chemistry , regioselectivity , hydrosilylation , silylation , organic chemistry , adduct , catalysis , radical , linoleic acid , fish oil , fatty acid , fish <actinopterygii> , fishery , biology
Hydrosilylation of fatty acid methyl esters (FAMEs) were efficiently catalyzed by Speier's and Wilkinson's catalysts in the case of vinylic acid esters, but less efficiently in the case of non‐vinylic ones, which gave non‐regiospecific additions. In the latter case, initiation by radicals led to regiospecific reactions for oleic esters (C10‐silylation). This regiospecificity can be attributed to the higher stability of the C10‐silylated adduct and of the corresponding radical intermediate. Only regioselective addition was observed for linoleic esters (C13‐silylation ≈ 70%, C10 ≈ 20%, C9 ≈ 10%). Molecular modeling was used to examine the stability of the isomeric products and radicals. The new concept of radical initiation sequence has been successfully applied to FAMEs and then was extended to crude fish oil. Copyright © 2001 John Wiley & Sons, Ltd.