Rhodium-catalyzed one pot synthesis of hydroxymethylated triglycerides

Abstract

International audienceno abstrac

Tertiary Amines as Ligands in a Four‐Step Tandem Reaction of Hydroformylation and Hydrogenation: An Alternative Route to Industrial Diol Monomers

“…These findings are also supported by recently shownr esults in ap arallel work. [42] To investigate the influence of solvents, polar protic solvents were used in this reaction and the hydroformylation activity was slightly inhibited, leading to am ix of TCD-dialdehyde 4 and TCD-diol 6 (entry 1.7-1.8). With polar aprotic solvents, only TCD-monoaldehyde 2 was obtained (entry 1.9-1.10) indicating that strong coordinating solvents, such as acetonitrile, have as trong binding character to the rhodium centre and deactivate the catalyst for the second hydroformylation.…”

“…Dependingo nt he size or sterical properties of the used amines, the capacity to form alcohols differs as with parallels tudies. [42] To further simplify the method, experiments in pure amine were performed at 70 bar.I tcould be shown that the reaction sequence is still feasible with 29 %y ield after 4h and 64 % yield after 16 hr eactiont ime for the desired diol 6 (Entry 1.12,1.13).…”

“…Despite the different substrates, the results of the optimisation of this paper are comparable to the results in ap arallel study. [42] The reaction sequence could be performed in pure amine to spare af urther solvent, and thus add to the overall efficiency of the process. The application of phosphines hindered the synthesis of alcohols.…”

“…Yields for the alcohol of 82 %w ere shown with styrene applying3 .75 mol % [RhCl(COD)] 2 and diamine ligand at ar eactiont emperature of 60 8Cafter 22 h. [41] Only recently,p arallel to our work Hapiotc o-worker studied the Rhodium-catalysed hydrohydroxymethylation of triunsaturated triglycerides with tertiary amines as ligands. [42] Selectivities of 95 %t owards the alcohols were shown with trihexylamine and N-methylpyrrolidine as ligandso ver 18 hr eaction time.…”

Robust Organocatalysts for the Cleavage of Vegetable Oil Derivatives to Aldehydes through Retrobenzoin Condensation

“…[4] Most of the reactions on oleochemicals occura tt he fatty acidc arboxy groupa nd they are comparatively few examples on the alkyl chain.H owever,t he presence of double bond(s) in unsaturated fatty acid derivatives allows the installation of arange of organic functions [5] including aldehyde, [6] epoxide, [7] diol, [8] ketone and diketone, [9] ahydroxyketone, [10] carbonate, [11] among others. [12] More importantly,c leavage reactions-mainly using methylo leate as the archetype-can give access to building-blocksw ith higher added value, essentially for surfactants and polymer applications. In this respect, the formation of fatty mono-a nd difunctionalized aldehydes is of great interesta st hey can be used for ab road variety of transformations.…”