Glutarate ester

Table 1. Enantioselective Hydrolysis of Malonate and Glutarate Esters...

The addition of ester enolates to oi.P-unsaturated esters occurs with identical diastereoselectivity as shown for a,(3-enones this is exemplified by the diastereoselective synthesis of erythro- and threo-2,3-disubstituted glutarate esters (178 and 179). 146 -c Similarly, Yamaguchi reports a general synthesis of /ra/tJ-2-alkoxycarbonyl-l-cycloalkanepropionates (181-184) from w-halo-a,(3-unsaturated esters (180),... 

Tertiary carbons are not carboxylated, however, so the rearrangement reaction can be of advantage for the synthesis of certain symmetrical glutaric esters (equation 68). 

Ring condensations with oxalic estor are Dilceto-cyclopentane dicarboxylic ester from oxalic and glutaric esters 25 COOCjH5 CHj—COOCjHj... 

COOCjHs CH.—COOCjHj By using /3/3-dimetliyl glutaric ester, Kommpa obtained diketo-apocainpliorie ester which was used for the synthesis of camphoric acid 2B COOCjllj CHj.COOC.jH5 CO—CH.COOCjII6... 

The hydroxyl group of this liydroxy-triiuetliyl glutaric ester is replaced by chlorine, this again by cyanogen, and the nitrile gives the required acid on hydrolysis, dl-campliorouic acid ... 

The condensation of tryptamine (XXVI) with the glutaric ester XCIX in the presence of Raney nickel and hydrogen yields a pair of isomeric lactams (Ca and Cb) of which the former on cyclization with phosphorus oxychloride followed by catalytic reduction gave the... 

Scheme 14. Synthesis of (-)-paroxetine using an asymmetric desymmetrization of a glutaric ester via enzymatic hydrolysis.

Ethyl acrylate will react with vinylic cuprates, but at a much slower rate than a, -unsaturated ketones and ethyl propynoates 205). Complex-ation with trimethyl phosphite is advantageous because the reactivities of the cuprate and resulting carbanion are increased. Glutarate esters are important by-products from the reaction of the intermediate carbanion with another molecule of the acrylate the primary addition product was obtained in yields from 3.4% to 38% and the glutarate ester in 7.1-31% yield. 

Treatment of bistrimethylsilyl enol ethers of glutaric esters with TiC leads to the stereoselective formation of rruns-1,2-cyclopropanedicarboxylic esters (equation 35). ... 

Dilithium enolates of glutaric esters undergo oxidative coupling to produce 1,2-cyclopropanedicarboxylic esters Cupric halides have been found to be the most satisfactory reagents for this coupling among various oxidants examined (equation 40) . ... 

Oxidative 1,3-coupling of dilithium enolates of glutaric esters gave cyclopropane-1,2-carb-oxylates, e. g. 12, in excellent yield. This reaction is accomplished with copper halides (copper(II) bromide or chloride). 

The utihty of Cu(II)-box complex 96 for asymmetric Mukaiyama-Michael reaction has been intensively studied by Evans et al. (Scheme 10.91) ]248]. In the presence of HFIP fhe 96-catalyzed reaction of S-t-butyl thioacetate TMS enolate with alkylidene malonates provides fhe Michael adducts in high chemical and optical yield. HFIP plays a crucial role in inducing catalyst turnover. Slow addition of the silyl enolate to a solution of 96, alkylidene malonates, and HFIP is important in achieving high yields, because fhe enolate is susceptible to protonolysis with HFIP in fhe presence of 96. The glutarate ester products are readily decarboxylated to provide chiral 1,5-dicarbonyl synthons. Quite recenfly, Sibi et al. reported enantioselective synthesis of t -amino acid derivatives by Cu( 11)-box-catalyzed conjugate addition of silyl enolates to aminomefhylenemalonates ]249]. 

The question of regiochemistry does not arise in the case of diesters. Diethyl succinate has been converted to the disilyl ketene acetal (59) in good yield. A number of glutarate esters (60) have been similarly transformed to (61). ... 

The reason why only the fluorinated ester drops spread over one of the fluorinated coatings can be explained by mutual attraction promoted by the structural and chemical affinity of the two fluorine-containing organic compounds. It had been established [5] that the fluorinated side chains of polymer S are sterically less closely packed and have more freedom of rotation than those of polymer A they may thus permit some lateral penetration of the closely related fluoro chains of the glutarate ester, whereas polymer A with its tight array of side chains is impervious to such penetration. The fluorinated ester exerts a slight solvent action on polymer S, but not on polymer A, when the polymer is totally immersed in the ester for periods longer than 10 days at ambient temperature, or 2 days at 50°C. 

M.J. Homan, R. Vail, B. Morgan, V. Sabesan, C. Levy, D.R. Dodds, A. Zaks, Enzymatic hydrolysis of a prochiral 3-substituted glutarate ester, an intermediate in the synthesis of an NKl/ NK2 dual antagonist, Adv. Synth. Catal. 343 (6-7) (2001) 744-749. 

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