Premium
Selective Ruthenium‐Catalyzed Hydroaminomethylation of Unsaturated Oleochemicals
Author(s) -
Cousin Kévin,
Hapiot Frédéric,
Monflier Eric
Publication year - 2020
Publication title -
european journal of lipid science and technology
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.614
H-Index - 94
eISSN - 1438-9312
pISSN - 1438-7697
DOI - 10.1002/ejlt.201900131
Subject(s) - ruthenium , chemoselectivity , rhodium , catalysis , regioselectivity , chemistry , acetonitrile , organic chemistry , phosphine , solvent , combinatorial chemistry
Rhodium‐catalyzed hydroaminomethylation (HAM) is recently described as an innovative way to functionalize triglycerides. In the search to reduce production costs, rhodium is sought to be replaced by ruthenium whose price is currently more than 20 times lower. In this study, HAM of unsaturated oleochemicals using ruthenium precursors is proceeded under phosphine‐free conditions. The experimental conditions are optimized by changing the nature of the solvent, the reaction temperature, and the CO/H 2 pressure. While rhodium leads to good catalytic activity and low chemoselectivity (mixture of hydroxyl and amino groups), ruthenium proves to be less active but more chemoselective as amino‐substituted products are mainly formed. Of interest, HAM of methyl 10‐undecenoate (MU) occurs in a highly chemo‐ and regioselective fashion using acetonitrile as solvent. Practical Applications : Selective Ru‐catalyzed hydroaminomethylation can be implemented on an industrial scale for the conversion of unsaturated oleochemicals into amines. This finding is of importance as the obtained amino‐products can be used in many industrial areas such as surfactants, polymers, or lubricants.