Catalytic C,C-Bond Forming Additions to Unsaturated Fatty Compounds

Abstract

A large number of novel fatty compounds have been synthesized by catalytic C,C-bond forming addition reactions to the C,Cdouble bond of unsaturated fatty compounds. Radical reactions such as the solvent-free addition of -halocarboxylic acid esters initiated by electron transfer, e.g., from copper to give fat-derived -lactones are described as well as Lewis acid-induced electrophilic addition reactions yielding new oleochemicals such as alkyl-substituted 4-chlorotetrahydropyrans, primary homoallylic alcohols, -, -unsaturated ketocarboxylic acids and Diels-Alder addition products. New catalysts as, e.g., ligandmodified rhodium catalysts for the hydroformylation and heterogeneous boron-modified rhenium catalysts for the olefin metathesis have been developed. The addition of C-nucleophiles such as dimethylmalonate and nitromethane is possible by palladium-(0)catalyzed additions to unsaturated fatty compounds after conversion of the electron-rich to an electron-poor double bond. More than fifty literature articles are reviewed.

Regio‐ and Stereoselective Diels–Alder Additions of Maleic Anhydride to Conjugated Triene Fatty Acid Methyl Esters

“…However, most of the electrophilic addition reactions as, for example, Friedel-Crafts acylations, Friedel-Crafts alkylations and ene additions to mono-unsaturated fatty compounds such as oleic acid gave 1:1 mixtures of two regioisomeric addition products, which could not be separated. [1,2] Solvent-free thermal reaction at 190°C of maleic anhydride and mono-unsaturated fatty acid methyl esters such as methyl oleate gave the respective ene-addition products as regioisomeric and diastereomeric mixtures. [3] Recently, we described highly regioselective carbon-carbon bond-forming additions to the reactive enyne system of methyl santalbate [methyl (E)-octadec-11-en-9-ynoate] [4] and highly regio-and diastereoselective Prins-type cyclizations of methyl ricinoleate [methyl (9Z,12R)-12-hydroxy-9-octadecenoate] with aldehydes.…”

“…[8] Punicic acid (9,13-cis,11-trans-octadecatrienoic acid) (3) is the main fatty acid of the seed oil of pomegranate [7] (Figure 1). (1), α-eleostearic acid (9-cis,11,13-trans-octadecatrienoic acid) (2) and punicic acid (9,13-cis,11-trans-octadecatrienoic acid) (3). In the experiments described in this article the respective methyl esters 1a, 2a and 3a were used.…”

Process Options for the Catalytic Conversion of Renewables into Bioproducts

“…Catalytic CaC coupling reactions of unsaturated fatty compounds have been reviewed by Biermann and Metzger [51]. Metathesis reactions involving unsaturated fatty compounds to prepare o-unsaturated fatty acid esters have been applied by Warwel et al [52].…”

Self-Metathesis of 1-Octene Using Alumina-Supported Re2O7 in Supercritical CO2

“…While many of the earlier publications relate to gasphase processes, where the olefins were passed through a catalyst bed, applications of the heterogeneous reaction system have been widened to the liquid-phase metathesis, involving liquid olefins such as among others: pentene, [7] a,x-olefins, [11] unsaturated nitriles, [12] octane [10,13,14] and oleochemicals [15][16][17]. In most cases the heterogeneous catalysts required activation, e.g.…”