Metal tartaric acid-modified nickel

Nickel and other transition metal catalysts, when modified with a chiral compound such as (R,R)-tartaric acid 5S), become enantioselective. All attempts to modify solid surfaces with optically active substances have so far resulted in catalysts of only low stereoselectivity. This is due to the fact that too many active centers of different structures are present on the surface of the catalysts. Consequently, in asymmetric hydrogenations the technique of homogeneous catalysis is superior to heterogeneous catalysis56). However, some carbonyl compounds have been hydrogenated in the presence of tartaric-acid-supported nickel catalysts in up to 92% optical purity55 . 

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). 

Until recently, access to optically active 3-hydroxyalkanoates by enantioselective transition metal catalysis was based primarily on the heterogeneous hydrogenation of 3-oxo esters by Raney nickel modified with tartaric acid and sodium bromide (see Section 2.3.1.1.). As far as homogeneous catalysis is concerned, the best optical induction (71 % ee) in the hydrogena-... 

Table 4.7. Rate of formation of (R)-(-)-MHB (mmol h g ) and ee values in the enantioselective hydrogenation of methyl acetoacetate on deposited nickel-kieselguhr catalysts, promoted with 1% noble metals and modified with (2R,3R)-tartaric acid (according to summarized data of Orito et al. ).

Orito, Y., Niwa, S., and Imai, S. (1976) As3munetric hydrogenation of methyl acetoacetate using Nickel-Platinum metal-Kieselguhr catalysts modified with tartaric acid, Yuki Gosei Kagaku Kiokaishi J. Synth. Org. Chem. Jpn.) 34, 236 - 239. 

In analyzing more than 250 publications Chapter 4 covers effective metal catalysts, mainly nickel, but also bimetal- and multimetal-systems, and their best modifiers, amino acids and tartaric acids. It is noted that it took more than 25 years to improve the modified nickel catalysts from their original poorly efficient systems into the modem excellent heterogeneous catalysts that hydrogenate carbonyl compounds with enantioselectivities of 96-98%. 

Alternatively, the surface of a metal can be modified with an enantiomerically pure additive. For example, in 1956 palladium metal/silk fibroin was used for the hydrogenation of alkenes with moderate enantioselectivity. However, most success with modified metal siufaces has been achieved in the hydrogenation of ketones. The reduction of 3-keto esters with a Raney nickel/tartaric acid/sodium bromide catalyst provides good enantioselectivities. For example, P-keto ester (3.108) affords the P-hydroxy ester (3.109). Platinum metal modified with cinchona alkaloids has been successfully used with a-keto esters. The reaction yields product with up to 90% ee in the reduction of a-keto ester (3.110). ... 

Catalysts modified by tartaric acid (commonly referred to as tartrate-modified catalysts) constitute the most extensively studied class of modified catalysts (Izuma, 1983 Bartok, 1985 Sachtler, 1985 Tai and Harada, 1986). The catalyst usually consists of Raney nickel or a noble metal-containing bimetallic system, modified by tartaric acid with NaBr as a comodifier in a mildly polar aprotic solvent such as methyl propionate (Izuma, 1983 Tai and Harada, 1986). The reaction is usually carried out in the temperature range 60-100 °C at 80-120 atm. 

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