Troger’s bases

The hydrogenation of ehtyl pyurvate (EtPy) was carried out at 23 °C in a SS autoclave equipped with an injection chamber for separate introduction of the modifier Cinchonidine (CD) and Troger s base (TB) was used as modifiers. Different batches of EtPy, (Fluka) and Pt/Al203 catalysts (Engelhard E 4759, 5 %w Pt, Dpt = 25 %) were used. Experimental details incliding GC analysis can be found elsewhere [3,12]. The optical yield was calculated as e.e. = ([R]-[S])/([R]+[S]). The e.e. values were corrected for the amount of racemic product formed in minor amount in the reactor prior to the injection of CD. 

Monte-Carlo simulation method was used to investigate the interaction of the [CDdosed-MePy] complexes with Pt (111) surface. The result shown in Figure 5 indicates that the shielded complex can maintain its entity even after adsorption. Further computer modeling indicated that there are other molecules with the ability to induce SE. In this respect Troger s bases are of particular interest. The calculated Troger s base-methyl pyruvate complex (R form) is shown in Figure 6. 

Figure 6, Troger s base-methyl pyruvate complex.

Table 1. Hydrogenation of ethyl puruvate in the presence of Troger s base...

Complexes (65) and (66) result from the reaction of IrCl3 with inah and PPh3 (inah = isonicotinic acid hydrazide).92 Reaction of Troger s base (tb) (67) with IrCl3 yields dark violet tb 2IrCl3 (6S).93 (68) was not catalytically active towards the hydrosilylation of alkynes. 

A similar reaction of thiophene analogues of Troger s base with formaldehyde was carried out by Kobayashi et al. <2002J (P1)1963>. 

Figure 3.12 Enantioseparation of TrOger s base on (a) microcrystalline cellulose triacetate (CTA I) and (b) 21 coated on silica gel. Column, 25 x 0.46 (i.d.) cm eluent ethanol-HoO (7/3) flow rate, 0.5 ml/min).

Figure 16.17 Amine-terminated polypropylene imine) dendrimers act as tridentate ligands for the complexation of transition metals [217] (a), and can function as templates for the assembly of Troger s base dizinc(ll) bis-porphyrin molecules, (b) [218]...

Kaupp G (2004) Troger s base derivatives. In Encyclopedia of supramolecular chemistry. Marcel Dekker, New York, pp 1516-1524... 

Troger s base, the resolution of which with a strongly acidic resolving agent is accompanied by a crystallization-induced asymmetric transformation (also see p426)87. 

Acids and bases. These can be converted to various salts. For example, the absolute configuration of dimethyl (M)-5,6,8,10-tetramethyl-l,2-heptalenedicarboxylate (p 404) was determined by X-ray analysis of its (+)-ephedrine salt84, and the absolute configuration of Troger s base (p 404) by X-ray analysis of a salt with an acid of known configuration87. 

In molecules in which the nitrogen atom is at a bridgehead, pyramidal inversion is of course prevented. Such molecules, if chiral, can be resolved even without the presence of the two structural features noted above. For example, optically active 12 (Troger s base)... 

This material has been successfully applied for the enantioseparation of Troger s base and tetrahydropalmatine, and for the separation of anaesthetic drugs, where the... 

CSPs (CTA-I and CTA-II) have inverse selectivity for Troger s base and trans-1,2-diphenyloxirane racemates. These characteristics of CTA CSPs are responsible for good chiral resolution of small cychc carbonyl compounds [42]. In 2001 Aboul-Enein and Ah [63] observed the reversed order of elution of nebivolol on a Chiralpak AD column when ethanol and 2-propanol were used separately as the mobile phases. Table 1 presents selectivity data for the polysaccharide-based CSPs. Okamoto et al. [42] observed that the introduction of a methyl group at the para position of cellulose tribenzoate results in a dramatic shift of the structural selectivity toward aromatic compounds with larger skeletons, and its selectivity was rather similar to that of cellulose tricinnamate. 

FIGURE 16 The chemical structures of some drugs resolved on different CSPs based on a- and /1-cyclodextrin derivatives (Fig. 15) Troger s base (I), tra .s-2,.1-diphenyloxirane (II), l-(9-anthryl)-2,2,2-trifluoroethanol (III), 1,2,2,2-tetraphenylethanol (IV), 2,2 -dihy-droxy-6,6-dimethylbiphenyl (V), 2-phenylcyclohexanone (VI), flavanone (VII), benzoin (VIII), and tnms -cyclopropanedicarboxylic acid anilide (IX). (From Ref. 49.)... 

Benzoin, methylbenzoin, ethylbenzoin, isopropylbenzoin, benzoin oxime, cyclobutyldianilide carbamate, 1,1 -binaphthyl-2,2 -diol, trans-stilbene oxide, and Trogers s base Polymethacrylate 104, 96... 

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