Solid support catalysts hydrogenation

Aqueous-biphasic and solid-supported catalysts for benzothiophene hydrogenation as a pretreatment for HDS... 

An alternative to the supported liquid phase (SLP) method was recently proposed using the same type of solid the supported hydrogen bonded (SHB) catalysts. First demonstrated with the zwitteronic Rh1 catalysts [(sulphos)Rh(cod)] (1) and [(sulphos)Rh(CO)2] (2) (sulphos = 03S(Cr,I I4)CI I2C(CH2PPh2) ). the immobilization procedure is based on the capability of the sulfonate tail of sulphos to link the silanol groups of the support via hydrogen bonds (Figure 12). 

Immobilized catalysts on solid supports inherently have benefits because of their easy separation from the products and the possibility of recycling. They are also expected to be useful for combinatorial chemistry and high-throughput experimentation. The polystyrene-bound BINAP/DPEN-Ru complex (beads) in the presence of (CH3)3COK catalyzes the hydrogenation of l -acetonaphthone with an SCR of 12 300 in a 2-propanol-DMF mixture (1 1, v/v) to afford the chiral alcohol in 97% ee (Fig. 32.35) [113]. This supported complex is separable... 

Scheme 39.7 Continuous-flow hydrogenation of dimethyl itaconate (15) using a solid-supported chiral catalyst and scC02 as the mobile phase (PTA= H3P40PW12).

In contrast, liquidiliquid phase-transfer catalysis is virtually ineffective for the conversion of a-bromoacetamides into aziridones (a-lactams). Maximum yields of only 17-23% have been reported [31, 32], using tetra-n-butylammonium hydrogen sulphate or benzyltriethylammonium bromide over a reaction time of 4-6 days. It is significant that a solidiliquid two-phase system, using solid potassium hydroxide in the presence of 18-crown-6 produces the aziridones in 50-94% yield [33], but there are no reports of the corresponding quaternary ammonium ion catalysed reaction. Under the liquidiliquid two-phase conditions, the major product of the reaction is the piperazine-2,5-dione, resulting from dimerization of the bromoacetamide [34, 38]. However, only moderate yields are isolated and a polymer-supported catalyst appears to provide the best results [34, 38], Significant side reactions result from nucleophilic displacement by the aqueous base to produce hydroxyamides and ethers. 

The SULPHOS-containing rhodium and ruthenium complexes retained their catalytic activity in heteroarene hydrogenation when supported on styrene-divinylbenzene polymer [180] or on silica [181], and showed even higher activity than in homogeneous solution. This effect is attributed to the diminished possibility of dimerization of the active catalytic species to an inactive dimer on the surface of the support relative to the solution phase. The strong hydrogen bonds between the surface OH-groups on silica and the -SO3 substituent in 31 withheld the catalyst in the solid phase despite the rather drastic conditions (100 °C, 30 bar H2). 

In order to increase the contact of a catalyst with hydrogen and the compounds to be hydrogenated platinum (or other metals) is (are) precipitated on materials having large surface areas such as activated charcoal, silica gel, alumina, calcium carbonate, barium sulfate and others. Such supported catalysts are prepared by hydrogenation of solutions of the metal salts, e.g. chloroplatinic acid, in aqueous suspensions of activated charcoal or other solid substrates [28. Supported catalysts which usually contain 5, 10 or 30 weight percent of platinum are very active, and frequently pyrophoric. 

---