Glutaric acid diethyl ester

Biocatalysis plays a central role in the manufacturing of statin side chains (Figure 6.2). A first set of approaches exploits enzymatic desymmetrization reactions, for example, of the methoxyacetyl ester of glutaric acid diethyl ester with commercially available a-chymotrypsin as explored by Ciba SC with a yield of 94% and enantiomeric excess of up to 98% [1]. In the optimized procedure, the substrate was available in a concentration of 1 M at an enzyme/substrate ratio of 7% (wt/wt), and the reaction took approximately a day. The subsequent steps to the final acetonide also involved a pig-liver esterase (PLE) catalyzed selective hydrolysis of the methoxyacetyl group (Figure 6.2a). 

In the collidine class there are possibly two groups, D and E (Fig. 4), capable of induction. The compound containing group E is )S-methyl glutaric acid diethyl ester. The compound containing groups D and E is DDC, a powerful inducer. 

The Michael reaction of nitriles with unsaturated carbonyl compounds was examined using the SA-NEtj catalyst As shown in Table 1.6, the SA-NEtj showed the highest catalytic activity for the Michael reaction of ethyl 2-cyanopropionate with ethyl acrylate to afibrd 2-cyano-2-methyl glutaric acid diethyl ester in 94% yield (entry 1). SiOj-NEtj was much less active under the reaction conditions (entry 2). Neither triethylamine nor sihca-alumina promoted the desired addition reaction (entries 3 and 4). Notably, the reaction scarcely proceeded with the... 

Amino-l-cyclohexylmethylphosphonic acid diethyl ester was utilized for the preparation of hapten 1, recently employed to induce the first monoclonal catalytic antibodies capable of catalyzing peptide bond formation[97]. The key steps of the synthesis of 1 include (a) preparation of scalemic a-aminophosphonate, (b) generation of the p-nitrobenzyl ester, (c) installation of a suitable second phosphonate ester linkage, (d) M-acylation with glutaric anhydride. 

The chiral complex 54, formed from LiAlFLj, (15,2/f)-(+)- or (l/f,2S)-(—)-iV-methyl-ephedrine (1 equiv.) and 3,5-dimethylphenol (2 equiv.) and originally introduced for the reduction of ketones with 15-80% e.e.s, has also been shown to reduce oximes of a-keto esters with good stereoselectivity. Applied to the reduction of diethyl 2-hydroxyimmo[4- " C]glutarate, it provided [4- " C]glutamic acid diethyl ester in >60% yield and 80% e.e. ". ... 

With diethyl malonate. Two different products are obtainable in moderate yield by reaction of malonic ester with formalin. With a 1 2 ratio of aldehyde to ester and diethylamine as catalyst, the product is the tetraester (1), an intermediate in one synthesis of glutaric acid. With a 2 1 ratio and potassium bicarbonate as catalyst, the product is the crystalline solid diethyl bis(hydroxymethyl)malonate (2). ... 

Oxalic esters added in small amounts, with ice-salt cooling, under H2, to Na-ethoxide in ether, then glutaric acid ester added, refluxed 1 hr., the ether distilled off, the mixture heated to 105°, and the resulting Na-compound decomposed in cold 20%-H2SO4 —diethyl cyclopentane-l,2-dione-3,5-dicarboxylate. Y 65 %. (G. Hesse and H. Bucking, A. 563, 31 (1949) f. e. s. G. Hesse and K. W. F. Bockmann, A. 563,37 (1949).)... 

The rates of alkaline hydrolysis of methyl pyridazine-3- and -4-carboxylate were correlated with those of pyridinecarboxylates and benzoates. Diethyl pyridazine-4,5-dicarboxylate (214) reacts with 1,3-diphenylguanidine in the presence of sodium hydride to give the spiro compounds 215, the structure of which was determined by X-ray analysis. Related spiro compounds were obtained from the above ester and esters of glutaric or acetonedicar-boxylic acids. 5-Aminopyridazine-4-carboxylic acid is simply synthesized from the 5-carboxamido analog by Hofmann rearrangement. ... 

Dichlorotoluene Diethyl ether Diethyl ketone Diethylene glycol Diethylene glycol methyl ether Diethylene glycol n-butyl ether Dimethyl esters of adipic, glutaric and succinic acids... 

Cyclic j -diketones from ketocarboxylic acid esters. Diethyl a-methyl-a-acetyl-glutarate in dry ether added dropwise with stirring to a suspension of alcohol-free K-ferf-butoxide in dry ether, and refluxed 3 hrs. -> ethyl l-methyl-2,4-dioxocyclohexane-l-carboxylate. Y 70.4%. S. M. Mukherji, R. K. Sharma, and O. P. Vig, Soc. 1958, 4770. 

---