A hydroaminomethylation/hydrohydroxymethylation sequence for the one pot synthesis of aminohydroxytriglycerides

Abstract

International audienceno abstrac

Selective Ruthenium‐Catalyzed Hydroaminomethylation of Unsaturated Oleochemicals

“…Generally speaking, we notice a lower catalytic activity of the Ru/amine combination by comparison with the Rh/amine couple in HAM of internal C5 5C bonds. [7] For example, under 80 bar CO/H 2 (1/1) at 110 C in toluene with HNBu 2 as amine, the turn-over frequency (TOF) is of 0.88 h À1 in HAM of T using Ru-catalyst while we obtained TOF of 3.7 h À1 with Rh-catalyst in our previous study. [7] Amongst the studied amines, acyclic ones are the more appropriate, probably because of their σ-donating ability towards ruthenium and the flexibility of their structure to fit the ruthenium coordination sphere.…”

“…[15,16] Reaction conditions were similar to previous studies on rhodium catalysts. [7] The first set of experiments concerned the amine nature ( Table 1). Indeed, during the course of the HAM reaction, amines may act as both reactants and ruthenium ligands.…”

“…[6] For example, we recently showed that phosphine-free HAM of triolein (T) and commercial oils resulted in the functionalization of fatty chains by amino and hydroxyl groups in various proportions depending on the applied experimental conditions. [7,8] To overcome the pricing hurdle of rhodium catalysts, rutheniumbased approaches were developed. Ruthenium was envisaged as an interesting surrogate because it is currently more than 20 times cheaper than rhodium.…”

Preparation and Spectroscopic Characterization of Si‐Coated Vegetable Oils and their Application in In Situ Curing of Hybrid Coatings

“…[9][10][11] Furthermore, researchers have investigated the modification of vegetable oils or fatty acids and other derivatives of oil with hetero-atoms to confer alternative properties. [15,16] Amine functional groups have been targeted with the goal of reaching hardeners for bio-based epoxy resins. [12][13][14] The insertion of nitrogen elements has also been investigated.…”

cRh‐Catalyzed Hydroformylation of Divinylglycol: An Effective Way to Access 2,7‐Dioxadecalin‐3,8‐diol

“…For example, hydroformylation appears as one of the most effective catalysed reaction as it is atom economic and provides aldehydes as useful intermediates , . Our team recently showed that triglycerides can be directly functionalized at their carbon–carbon double bonds to form valuable compounds through hydrohydroxymethylation (HHM) or hydroaminomethylation (HAM) , . The present study sought to address the use of a rhodium‐catalyst to convert DVG into a series of DVG derivatives under hydroformylation conditions.…”