Hydrogenation catalysis pathways

The concept of alternative reaction pathways leads to the concepts of selectivity and stereospecificity in hydrogenation catalysis. 

Radical pathways in hydrogenation catalysis by 14.3.2.1. Thermodynamics of Hj addition to ... 

An article is exclusively focused on outer sphere catalysts. In outer-sphere hydrogen catalysis, substrates such as ketone, imine, or A-heterocycle remain in the outer sphere. A hydride and a proton are transferred to these substrates by either a concerted or a stepwise path from catalysts such as Bullock s ionic hydrogenation catalysts, bifunctional catalysts in the tradition of Shvo and Noyori, and Stephan s frustrated Lewis pair catalysts. The outer-sphere pathways can use inexpensive metals and even non-metal catalysts, and lead to useful selectivity properties, particularly Noyori s asymmetric catalysis. ... 

Wawzonek et al. first investigated the mechanism of the cyclization of A-haloamines and correctly proposed the free radical chain reaction pathway that was substantiated by experimental data. "" Subsequently, Corey and Hertler examined the stereochemistry, hydrogen isotope effect, initiation, catalysis, intermediates, and selectivity of hydrogen transfer. Their results pointed conclusively to a free radical chain mechanism involving intramolecular hydrogen transfer as one of the propagation steps. Accordingly, the... 

In the M. capsulatus (Bath) system, all three components are necessary to obtain turnover with NADH as the reductant (57). With the M. trichosporium OB3b system, protein B is apparently not required (27). Instead, in this latter system, protein B increases the initial rates of the catalytic hydroxylation reaction (27). Catalysis can be achieved by means of a shunt pathway with hydrogen peroxide and Hox alone from both organisms (58-60). The efficiency of the shunt pathway, however, varies significantly. With M. trichosporium OB3b, alcohol yields greater than those obtained with the completely reconstituted system have been observed (58). Furthermore, upon addition of protein... 

Takanabe, K. Aika, K.-I. Inazu, K. T. B. Seshan, K. Lefferts, L., Steam reforming of acetic acid as a biomass derived oxygenate Bifunctional pathway for hydrogen formation over Pt/ZrOz catalysts. Journal of catalysis 2006,243(2), 263-269. 

Control of the multitude of pathways which feed molecules can take is the primary objective of aU catalyst and process developments. The work covered in this chapter focuses primarily on describing the approaches in material and catalysis development which have led to major advances in zeolite application in hydrocarbon conversion. The breaking and formation of carbon-carbon and carbon-hydrogen bonds constitute the majority of the chemical transformations involved here with the less prevalent, but very important, breaking of carbon bonds with sulfur, nitrogen and oxygen taking place in parallel. 

In non-polar solvents many aminolysis reactions show a third-order dependence on the amine, B. This may be explained by catalysis of leaving-group departure by hydrogen-bonded homoconjugates, BH+B. Evidence for this pathway has been adduced from studies of the reactions of some nitro-activated (9-aryl oximes (7) with pyrrolidine in benzene, chlorobenzene, and dioxane, and with piperidine and hexylamine in cyclohexane. The third-order dependence on amine of the reaction of 2,6-dinitroanisole with butylamine in toluene and toluene-octanol mixtures has been interpreted in terms of a mechanism involving attack by dimers of the nucleophile. ... 

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