Patai S., Rappoport Z. 1997 The chemistry of functional groups. The chemistry of double-bonded functional groups / 0843 908

described in detail461. Lower ee (63%) was observed in the case of the hydrogenation of 2-butanone460. 2-Butanol of 72% optical purity was, however, obtained466 by optimizing the reaction variables (solvent, carboxylic acid as co-modifier, reaction temperature, amount of TA NaBr MRNi, pivalic acid/2-butanone ratio) and modification variables (NaBr/TA ratio, pH, amount of modifying solution). The degree of the intrinsic enantiodifferentiating ability of the adsorbed TA for 2-butanone was supposed to be similar to the ability of TA for higher 2-alkanones.

The enantio-differentiating hydrogenation of 3-octanone467 carried out with TA NaBr MNi catalyst was compared with that of 2-alkanones. Significant differences were observed. For example, the hydrogenation of 3-octanone on a TA NaBr-modified fine nickel powder resulted in a better optical yield (30%) than over a similarly modified Raney nickel. In addition, the hydrogenation at a lower temperature resulted in a lower optical yield in the hydrogenation of 3-octanone, whereas the optical yield was higher in the hydrogenation of 2-alkanones.

The differentiation between methyl and other alkyl groups takes place as follows467. First TA forms an associative complex on the catalyst surface with pivalic acid added to the reaction system462. The substrate is adsorbed to the catalyst surface through TA. The TA pivalic acid complex recognizes the structure of the substrate through an interaction between the alkyl group of pivalic acid and that of 2-alkanones. Finally, hydrogen adds to the substrate from the catalyst surface. This enantio-differentiating model for the hydrogenation of 2-alkanones is given in Figure 1468.

According to this model, the carboxylic acid added to the reaction system is the key factor for achieving the enantio-differentiating hydrogenation of 2-alkanones. Therefore, more detailed comparative studies of the enantio-differentiating hydrogenation of 2- and 3-alkanones, including the structure of the carboxylic acid added to the reaction system, would lead to the development of highly efficient heterogeneous catalysts for the enantiodifferentiating hydrogenation of 3-alkanones. In addition, factors necessary to differentiate between various alkyl groups can be recognized.

Enantioselective heterogeneous catalytic hydrogenation of acetophenone469 471 to (R)- (C)-1-phenylethanol (ee 20%) in the presence of (S)-proline (the chiral auxiliary) was investigated. The effect of various catalytically active metals (Pt, Rh, Raney Ni, Pd), the reaction temperature and the amount of catalyst on the optical purity was studied. The correlation between the optical yield and the conversion, the concentration of the reactants, different pretreatment methods and additives was also investigated469 (equation 49).

Pivalic acid Na+

−

(R, R)-Tartaric acid

Of the ˛,ˇ-unsaturated ketones only the chiral hydrogenation of isophorone (3,3,5- trimethyl-2-cyclohexen-1-one) was investigated470 473. The effects of catalyst, pH, hydrogen pressure and intensity of agitation on the enantioselective hydrogenation of isophorone were discussed. The changes in chemical and optical yields of the saturated ketone as a function of conversion and the water content of the solvent were also investigated. An iminium salt intermediate (41) undergoing hydrogenation was indentified472 (equation 50). The reaction product was (S)-3,3,5-trimethylcyclohexanone (ee 60%), and an alkylated proline side product was also formed.

O

+

Note that there are virtually no data for the asymmetric hydrogenation of the CDC bond over heterogeneous catalysts. The first example474 described the chiral hydrogenation of ˛-phenylcinnamic acid with 15% ee.

The hydrogenation of isophorone and acetophenone in the presence of (S)-proline shows some similarities. The effect of Pd C (S)-proline system is based on the addition reaction of the reactants and (S)-proline in solution and on the chemoselectivity of Pd. Both hydrogenations should be termed diastereoselective rather than enantioselective, since the asymmetric induction takes place in the adduct molecules.

A relatively small number of examples have appeared on the asymmetric hydrogenation of imines, oximes and hydrazones without any other functionality, though the resulting optically active amines are synthetically important compounds. In contrast, many more publications deal with the asymmetric hydrogenation of compounds with CDN bond containing other functional groups. This is mainly due to the importance of ˛-amino acids. On the other hand, the prochiral substrate must be a bifunctional compound possessing a hydrogenation site and a binding site in order to get high enantioselectivity.

There are detailed summaries treating the asymmetric hydrogenation of such bifunctional compounds315,455,475. The present review, consequently, deals only with the asymmetric hydrogenation of compounds in which the CDN bond is the sole functional group.

The chiral hydrogenation of ketimines can be performed either by the hydrogenation of compounds containing a chiral auxiliary group on achiral catalysts, or by hydrogenating achiral ketimines on chiral catalysts. Some examples for diastereoselective hydrogenation of ketimines can be seen in equations 51 53.

Me

(44)

The formation of chiral, enantio-enriched imines by the utilization of optically active amines, and the subsequent hydrogenation of the diastereotopic imine faces provides a powerful method for the introduction of new stereogenic centers, often with high diastereomeric excesses. New, optically active amines are then obtained by the removal of the chiral auxiliary group475. Thus, the condensation of 2-alkylcyclohexanones with optically active 1-phenylethylamine yielded the mixture of imines 42 and 43 which were hydrogenated over Raney Ni to give essentially only one optically active, diastereomerically

enriched cis secondary amine 44 in good yield476. These results require that an asymmetric interconversion of the diastereomeric imines (42, 43) occurs prior to hydrogenation and that either the diastereomer 43 is greatly favored at equilibrium or that the reduction rate of 43 (or its conformational isomer) is much faster than that of 42. The same method was applied in the transformation of 2-alkylcyclopentanones477.

active 1-phenylethylamine of substituted acetophenones via the corresponding imines (equation 52).

H

(52) Diastereoselective hydrogenation of N-isobornylcamphor imine has also been utilized

to prepare the useful optically active diisobornylamine (equation 53)480.

N

H

No new literature data are available for the asymmetric hydrogenation of ketimines without any other functionality.

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