Enantioselective support quartz

For the Pd-silk catalyst,2 PdCl2 was deposited on silk and reduced to Pd° moderate enantioselectivities were obtained for the hydrogenation of a C=C bond (66% enantiomeric excess, ee, which is the difference between enantiomers divided by the sum of enantiomers), but the silk support presented two problems it tended to deteriorate with time on stream and it varied from source to source, so enantioselectivities were not reproducible (Scheme 3.2). On the other hand, deterioration was not a problem with the metal-quartz catalysts. 

The first reported attempts of what was then called "absolute or total asymmetric synthesis" with chiral solid catalysts used nature (naturally ) both as a model and as a challenge. Hypotheses of the origin of chirality on earth and early ideas on the nature of enzymes strongly influenced this period [15]. Two directions were tried First, chiral solids such as quartz and natural fibres were used as supports for metallic catalysts and second, existing heterogeneous catalysts were modified by the addition of naturally occuring chiral molecules. Both approaches were successful and even if the optical yields were, with few exceptions, very low or not even determined quantitatively the basic feasibility of heterogeneous enantioselective catalysis was established. 

Schwab et al. (46, 47) showed that nickel, copper and platinum supported on optically-active quartz behave as enantioselective catalysts for the dehydrogenation and oxidation of racemic sec-butyl alcohol. At low conversion, a measurable optical rotation of the reaction solution is observed, showing that one enantiomer has reacted... 

This chapter summarizes data about the application of chiral metal catalysts supported on optically active quartz crystals in hydrogenation and other reactions. Despite the low enantioselective efficiency of these catalysts, recent result show that almost 100% enantioselectivity results when they are involved in autocatalytic processes. 

An early approach toward chiral heterogeneous catalysts was the deposition of the catalyticaUy active metal or metal oxide particles onto intrinsically chiral supports such as quartz [24], cellulose [25], or synthetic chiral polymers [26-28]. Hydrogenation and dehydration reactions were tested, but enantioselective performance was found to be poor. In a recent review, Mallat et al. [29] attributed this poor enantioselectivity to the fact that only a small fraction of the metal atoms would... 

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