Metals chiral modification

The modification of platinum-group metals by adsorbed chiral organic modifiers has emerged as an efficient method to make catalytic metal surfaces chiral. The method is used to prepare highly efficient catalysts for enantioselective hydrogenation of reactants with activated C = O and C = C groups. The adsorption mode of the chiral modifier is crucial for proper chiral modification of the active metal surfaces. The most efficient chiral modifiers known today are cinchona alkaloids, particularly CD, which yields more than 90% enantiomeric excess in the hydrogenation of various reactants. 

Reviews on stoichiometric asymmetric syntheses M. M. Midland, Reductions with Chiral Boron Reagents, in J. D. Morrison, ed., Asymmetric Synthesis, Vol. 2, Chap. 2, Academic Press, New York, 1983 E. R. Grandbois, S. I. Howard, and J. D. Morrison, Reductions with Chiral Modifications of Lithium Aluminum Hydride, in J. D. Morrison, ed.. Asymmetric Synthesis, Vol. 2, Chap. 3, Academic Press, New York, 1983 Y. Inouye, J. Oda, and N. Baba, Reductions with Chiral Dihydropyridine Reagents, in J. D. Morrison, ed., Asymmetric Synthesis, Vol. 2, Chap. 4, Academic Press, New York, 1983 T. Oishi and T. Nakata, Acc. Chem. Res., 17, 338 (1984) G. Solladie, Addition of Chiral Nucleophiles to Aldehydes and Ketones, in J. D. Morrison, ed., Asymmetric Synthesis, Vol. 2, Chap. 6, Academic Press, New York, 1983 D. A. Evans, Stereoselective Alkylation Reactions of Chiral Metal Enolates, in J. D. Morrison, ed., Asymmetric Synthesis, Vol. 3, Chap. 1, Academic Press, New York, 1984. C. H. Heathcock, The Aldol Addition Reaction, in J. D. Morrison, ed., Asymmetric Synthesis, Vol. 3, Chap. 2, Academic Press, New York, 1984 K. A. Lutomski and A. I. Meyers, Asymmetric Synthesis via Chiral Oxazolines, in J. D. Morrison, ed., Asymmetric Synthesis, Vol. 3, Chap. 

Generally, a homoorganocopper reagent has two different metals in the cluster. Their chiral modification needs a chiral ligand whose heteroatoms coordinate selectively to copper and other metals. The first approach along this line was reported by Kretchmer, who used chiral natural diamine 7 as a ligand for methyl-copper in the reaction with cyclohexenone to afford the adduct in only 6% ee [49]. 

The history of heterogeneous enantioselective catalysis with chiral modification of the metal surface extends back even further than that of homogeneous molecular metal catalysis. However, successful precedents which result in a practicably useful stereoselectivity (e.g. of over 80%) involve only three types, all of which involve the hydrogenation of unsaturated bonds. Initially, these reactions were realized by achieving the correct solution to address all requirements for the chiral modifier. That is, the adsorption of the modifier must occur on all of the active... 

Fig. 1 Strategy of chiral modification of alkaline-earth metals...

The manifold chiral information readily available in customary carbohydrates provides an attractive approach to a chiral modification of metal carbenes that may be applied to either metal-mediated stereoselective organic synthesis via sugar auxiliaries or to carbohydrate synthesis via organometallic methodologies [107, 108]. The sugar moiety can be incorporated into metal carbenes by well-established procedures such as nucleophilic addition to the metal-coordinated carbene carbon atom or conjugate addition to the vinylogous position in alkenyl or alkynyl car-... 

Enzyme-mediated oxidation reactions offer highly diverse options for the modification of existing functional groups as well as for the introduction of novel function in chiral catalysis. Biooxidations often enable us to obtain complementary solutions to metal-assisted transformations and organocatalysis and are considered one of the important strategies of green chemistry . 

The use of chiral diaminocarbenes as transition metal hgands for catalyzed asymmetric synthesis is certainly an emerging field of research. They are relatively easy to prepare and they allow munerous structural modifications. Their transition metal complexes shows very usefull properties such as the thermal and air stability. Even if there is only a few reports of effective asymmetric transformations promoted by these class of catalyst, all these pioneering works open the route to the discovery of efficient new catalysts. 

Among the various strategies [34] used for designing enantioselective heterogeneous catalysts, the modification of metal surfaces by chiral auxiliaries (modifiers) is an attractive concept. However, only two efficient and technically relevant enantioselective processes based on this principle have been reported so far the hydrogenation of functionalized p-ketoesters and 2-alkanons with nickel catalysts modified by tartaric acid [35], and the hydrogenation of a-ketoesters on platinum using cinchona alk oids [36] as chiral modifiers (scheme 1). 

Synthesis of optically pure compounds via transition metal mediated chiral catalysis is very useful from an industrial point of view. We can produce large amounts of chiral compounds with the use of very small quantities of a chiral source. The advantage of transition metal catalysed asymmetric transformation is that there is a possibility of improving the catalyst by modification of the ligands. Recently, olefinic compounds have been transformed into the corresponding optically active alcohols (ee 94-97%) by a catalytic hydroxylation-oxidation procedure. 

Ph2P(NH2)NP(NH2)Ph2]+Cl, 19, which is prepared by the reaction of Ph2PCl3 and ammonia (136). This synthon has a preformed N-P-N-P-N unit and can be readily cyclized to a six or higher membered ring upon reaction with an appropriate reagent (137). An important application of the use of the Bezman s salt approach has been the synthesis of metallocyclophosphazenes of the type 20, which contain an early transition metal in the framework of the cyclophosphazene skeleton [Fig. 15(A)] (138). A modification of the Bezman s salt to design a chiral synthon allowed the synthesis of an optically pure cyclophosphazene (139). 

Modification of clays with metal complexes containing chiral ligands can be used for the preparation of catalysts for asymmetric reactions. Since the modified clays have limited interlayer space, the interaction between chiral ligands and substrates can be enforced and this may enhance the selectivity.203,204... 

Sherrington et al. were the first to attempt the synthesis of chiral polymeric metal complexes by the chemical modification route,78,177,178 whereby the [Mn(salen)Cl] units are attached in a pendant fashion, by only one of the aromatic rings, to poly(styrene) or poly(methacrylate) resin beads of various morphology. Epoxidation of 1-phenylcyclohexene gave enantioselectivity values between 61% and 91%. 

Epoxidation using a chiral fructose-derived ketone is easy to carry out, as it occurs in aqueous conditions. The reactions were performed without any modification of the published procedure. The glassware has to be free of trace metal, which can decompose the oxone the use of a plastic spatula is recommended and the volumes must be measured using glass-graduated cylinders. Table 6.2 gives different examples of epoxides which can be obtained using the method prescribed. 

Modification of catalytic metal surfaces with chiral natural compounds has led - for particular combinations - to results varying from good to excellent in enantioselective hydrogenations. The field has been reviewed [39]. 

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