A self-emulsifying catalytic system for the aqueous biphasic hydroformylation of triglycerides

Abstract

The Rh-catalyzed hydroformylation of the CC double bonds of triglycerides (T) was performed in aqueous medium through the formation of supramolecular complexes resulting from the inclusion of the alkenyl chains of T into the cavity of modified cyclodextrins (CDs).

Supramolecular Approaches To Control Activity and Selectivity in Hydroformylation Catalysis

“…In pioneering work by Monflier and co-workers, cyclodextrins have been applied in combination with water-soluble rhodium phosphine-based catalysts for biphasic hydroformylation of higher olefins . The cyclodextrin cavity is essentially hydrophobic and can therefore host various organic molecules in water (Figure ).…”

“…In pioneering work by Monflier and co-workers, cyclodextrins have been applied in combination with water-soluble rhodium phosphine-based catalysts for biphasic hydroformylation of higher olefins. 73 The cyclodextrin cavity is essentially hydrophobic and can therefore host various organic molecules in water ( Figure 14 ). Generally, the cyclodextrin host forms a water-soluble host–guest complex with the substrate, thereby increasing the water solubility of the alkene.…”

Synthesis of Nixantphos Core-Functionalized Amphiphilic Nanoreactors and Application to Rhodium-Catalyzed Aqueous Biphasic 1-Octene Hydroformylation

“…The efficient extension of aqueous biphasic catalysis to hydroformylation of higher α-olefins remains an outstanding challenge, despite several approaches having been proposed and studied. These approaches are surveyed in several recent reviews [11][12][13][14], and include the addition of modifiers or compatibilizers [15] such as cosolvents (mostly methanol, ethanol) [16][17][18][19][20][21][22], amphiphilic/thermo-regulated ligands and cyclodextrins [23][24][25] to improve mass transport as well as surfactants (cationic, anionic, double long chain cationic) to increase the interfacial area by emulsion and microemulsion methods [26][27][28][29][30][31][32][33][34][35][36][37]. Other interesting approaches apply thermomorphic methods with catalyst anchoring on lower critical solution temperature (LCST) polymers that become lipophilic at high temperatures [38][39][40][41][42][43][44][45] and on micellar formation with catalyst anchoring on the hydrophobic tail of surfactants [46][47][48].…”

Homogeneous hydroformylation of long chain alkenes catalyzed by water soluble phosphine rhodium complex in CH3OH and efficient catalyst cycling

“…Aqueous-organic biphasic catalysis possessing many advantages such as convenient separation of product, environmentally friendly and economy, [15][16][17][18][19][20][21][22] was successfully applied to the hydroformylation of ethene and propene on plant because their solubilities in the aqueous phase are sufficient to allow the hydroformylation to occur at an acceptable rate without phase-transfer limitations. Nevertheless, long chain alkenes (pC 6 ) have signicantly lower solubility in the aqueous solution of the catalyst, which correspondingly leads to lower reaction rates in aqueous-organic biphasic systems, making it difficult and economically unviable.…”