Reduction reactions, fine chemical

Creyghton, E. J., Van derWaai, J. 0. Meenwein-Ponndorf-Verley reduction, Oppenauer oxidation, and related reactions. Fine Chemicals through Heterogeneous Catalysis 2001,438-448. 

As mentioned earlier, a major cause of high costs in fine chemicals manufacturing is the complexity of the processes. Hence, the key to more economical processes is reduction of the number of unit operations by judicious process integration. This pertains to the successful integration of, for example, chemical and biocatalytic steps, or of reaction steps with (catalyst) separations. A recurring problem in the batch-wise production of fine chemicals is the (perceived) necessity for solvent switches from one reaction step to another or from the reaction to the product separation. Process simplification, e.g. by integration of reaction and separation steps into a single unit operation, will provide obvious economic and environmental benefits. Examples include catalytic distillation, and the use of (catalytic) membranes to facilitate separation of products from catalysts. 

In the different volumes of this new series we will feature catalysts for oxidation and reduction reactions, hydrolysis protocols and catalytic systems for carbon-carbon bond formation inter alia. Many of the catalysts featured will be chiral, given the present day interest in the preparation of single-enantiomer fine chemicals. When appropriate, a catalyst type that is capable of a wide range of transformations will be featured. In these volumes the amount of practical data that is described will be proportionately less, and attention will be focused on the past uses of the system and its future potential. 

A typical probe reaction for estimating catalytic properties in selective hydrogenations is the hydrogenation of cinnamaldehyde. This molecule contains both a C=C and a C=0 double bond, thus the formation of hydrocinnamaldehyde and/or cinnamyl alcohol by reduction of the one or the other, or the formation of phenyl propanol in the case of complete reduction may indicate the potential of the catalyst for other fine chemical transformations. Indeed, this reaction was one of the first to be tested by CNT-supported catalysts [120]. Noble metals show a high activity in this reaction and... 

Given the wide utility of biocatalysis in the fine chemical industry, why is there such an in-house reliance on classical methods of enantioseparation In fact, why is biocatalysis not applied more generally as a replacement for atom-inefficient or hazardous reactions that are intensively used in the pharmaceutical industry, such as amidation, reduction and oxidation ... 

Thus, in the fine chemicals industry, reduction of ketones and aldehydes relies mainly on the use of complex metal hydrides that require time-consuming workup of reaction mixtures and produce significant amounts of inorganic and organic wastes. Similarly, the oxidation of alcohols into carbonyls is traditionally performed with stoichiometric inorganic oxidants, notably Cr(VI) reagents or a catalyst in combination with a stoichiometric oxidant [1]. 

Heterogeneous copper catalysts prepared with the chemisorption-hydrolysis technique are effective systems for hydrogen transfer reactions, namely carbonyl reduction, alcohol dehydrogenation and racemization, and allylic alcohol isomerization. Practical concerns argue for the use of these catalysts for synthetic purposes because of their remarkable performance in terms of selectivity and productivity, which are basic features for the application of heterogeneous catalysts to fine chemicals synthesis. Moreover, in all these reactions the use of these materials allows a simple, safe, and clean protocol. 

The environmental and economical benefits of one-pot catalytic fine chemical syntheses, in which various successive chemical steps are accomplished in the same reaction vessel, generally over a bifunctional (or multifunctional) catalyst, are obvious. The reduction in the number of synthetic and separation steps has various positive consequences environmentally more sustainable processes (higher atom economy and lower environmental factors), lower operating costs, lower production of wastes and in general an improvement in the safety conditions.[1 31 The environmental advantages are still more remarkable when the transformation of renewable raw materials, such as mixtures of natural terpenes or carbohydrates are concerned. 

This reaction looks attractive because triethylsilane is non toxic and its by-products are low boiling point compounds easily removed by distillation. However, the alkanethiols have a strong bad smell and the remaining traces could be difficult to eliminate from the solution in certain cases, which make them undesirable in the synthesis of fine chemicals. Therefore, it appeared of interest to test the use of thiols supported on polyHIPE in these radical chain reductions. 

---