8- pentanedioic

Figure 11.1 Py/methylation GC/MS chromatograms of lead white pigmented linseed oil paint after 610 °C Curie point pyrolysis assisted with on line methylation using 2.5% methanolic TMAH (the sample and TMAH solution was applied onto a rotating Curie point wire pyrolysis time 6 s, interface 180°C). 1, heptenoic acid, methyl ester 2, heptanoic acid, methyl ester 3, butenedioic acid, dimethyl ester 4, butanedioic acid, dimethyl ester 5, octenoic acid, methyl ester 6, octanoic acid, methyl ester 7, pentenedioic acid, dimethyl ester 8, pentanedioic acid, dimethyl ester 9, nonanoic acid, methyl ester 10, hexanedioic acid, dimethyl ester 11, decanoic acid, methyl ester 12, heptanedioic acid, dimethyl ester 13, octanedioic acid, dimethyl ester 14, 1,2 benzenedicarboxylic acid, dimethyl ester 15, a methyl octanedioic acid, dimethyl ester 16, nonanedioic acid, dimethyl ester 17, a methoxy octanedioic acid, dimethyl ester 18, a methyl nonanedioic acid, dimethyl ester 19, a,a dimethyl nonenedioic acid, dimethyl ester 20a, a methyl nonenedioic acid, dimethyl ester 20b, a,a dimethyl nonanedioic acid, dimethyl ester 21, decanedioic acid, dimethyl ester 22, a methoxy nonanedioic acid, dimethyl ester 23, a methyl decan edioic acid, dimethyl ester 24, undecanedioic acid, dimethyl ester 25, a methoxy decan edioic acid, dimethyl ester 26, pentadecanoic acid, methyl ester 27, dodecanedioic acid, dimethyl ester 28, hexadecanoic acid, methyl ester 29, heptadecanoic acid, methyl ester 30, octadecanoic acid, methyl ester 31,8 methoxy 9 octadecenoic acid, methyl ester 32, 11 methoxy 9 octadecenoic acid, methyl ester 33, 9 methoxy 10 octadecenoic acid and 10 methoxy 8 octadecenoic acid 34, 9 oxo octadecanoic acid, 10 oxo octadecanoic acid 35, 9 epoxy octadecanoic acid 36, eicosanoic acid, methyl ester 37, 9,10 dimethoxy octadecanoic acid, methyl ester 38, docosanoic acid, methyl ester. Reprinted from J. Anal. Appl. Pyrol., 61, 1 2, van den Berg and Boon, 19, Copyright 2001, with permission from Elsevier...

Closely related to enolate additions to enones is the diastereoselective 1,4-addition of lithium enolates of esters, thioesters and amides to a,/ -unsaturated esters. These reactions provide syn-or ar /-2,3-disubstituted glutarates (pentanedioates). 

As an alternative to lithium enolates. silyl enolates or ketene acetals may be used in a complementary route to pentanedioates. The reaction requires Lewis acid catalysis, for example aluminum trifluoromethanesulfonate (modest diastereoselectivity with unsaturated esters)72 74 antimony(V) chloride/tin(II) trifluoromethanesulfonate (predominant formation of anti-adducts with the more reactive a,/5-unsaturated thioesters)75 montmorillonite clay (modest to good yields but poor diastereoselectivity with unsaturated esters)76 or high pressure77. 

An efficient synthesis of optically active pentanedioates is possible using ester enolates based on chiral alcohols. This is illustrated by the addition of the lithium (fl-cnolate of (1 R,2S,5R)-5-methyl-2-(1-methyl-l-phenylethyl)cyclohexyl propanedioate to methyl ( )-2-butenoate at — 100 °C which shows simple and induced diastereoselectivity. 

A variety of chiral amides as well as oxazolidones388 and imidazolidones389,390 may easily be prepared from amino alcohols that are derived from amino acids391 392. The addition of the lithium enolates of these amides under kinetically controlled conditions to a,/i-unsaturated esters yields optically active pentanedioates. Both syn- and //-5-amino-5-oxopcntanoates may be obtained with good diastereomeric ratios192. 

Glutanc acid [Pentanedioic acid], 98 Glycine,jV-glycyl-, ethyl ester, monohydro-chlonde, 89... 

Ethanedioic (oxalic) Propanedioic (malonic) Butanedioic (succinic) Pentanedioic (glutaric) Hexanedioic (adipic) Heptanedioic (pimelic) Octanedioic (suberic) Nonanedioic (azalic) Decanedioic (sebacic) Undecanedioic Dodecanedioic Phthalic Isophthalic Terephthalic 1,4-Naphthalic... 

The application of 3-aminopropyl phosphine (3) [41,46] as a building block for incorporation into -COOH functionalized frameworks provides an excellent example of the utility of preformed primary phosphine frameworks (Scheme 8) [46]. The reactions involved Michael addition of ferf-butyl acrylate to malonic acid dimethyl ester to produce the intermediate adduct, 2-methoxycarbonyl-pentanedioc acid 5-ferf-butyl ester 1-methyl ester, which upon treatment with trifluro-acetic acid (TFA) produced the corresponding diester acid,2-methoxy-carbonyl-pentanedioic acid 1-methyl ester, in near quantitative yield. It is remarkable to note that the reaction of NH2(CH2)3PH2 (3) with the diester acid is highly selective as the -COOH group remained unattacked whereas the reaction occurred smoothly and selectively at the -COOMe groups to pro-... 

TFA) in DCM (dichloromethane). Linkers for carboxylic acids have also been designed to effect cleavage via photolysis (3-nitro-4-hydroxymethylbenzoic acid, ONb 14) [18] and flouridolysis (N-3 or 4) ((4-hydroxymethyl)-phenoxy-t-butylphenylsilyl)phenyl pentanedioic acid monoamide (PBs) 15 [19] and quinonemethide-based handle 16 [20] (Fig. 

Mullen DG, Barany G. A new fluoridolyzable linkage for orthogonal solid-phase peptide synthesis Design, preparation, and application of the N-(3 or 4)((4-hydroxymcthyl)-phcnoxy-/butylphenylsilyl)phcnyl pentanedioic acid monoamine (Pbs) handle. J Org Chem 1988 53 5240-5248. 

Although the Ag(I)-catalyzed reaction of 46 leads exclusively to the cyclobutene isomer (47), the conversion of 46 into benzo[6]thiepin has been realized by a rhodium catalyst41). Treatment of 46 with a catalytic amount of dicarbonyl-2,4-pentanedio-natorhodium(I) in chloroform at 0 °C readily gives 57 % of 4 as pale yellow needles of... 

The [4+ 4]-homolog of the [4 + 2]-Alder-ene reaction (Equation (48)) is thermally forbidden. However, in the presence of iron(m) 2,4-pentanedioate (Fe(acac)3) and 2,2 -bipyridine (bipy) ligand, Takacs57 found that triene 77 cyclizes to form cyclopentane 78 (Equation (49)), constituting an unprecedented formal [4 + 4]-ene cycloisomerization. The proposed mechanism for this transformation involves oxidative cyclization followed by /3-hydride elimination and reductive elimination to yield the cyclized product (Scheme 18). 

HOOC -(CI lg-COOH Glutaric acid Pentanedioic acid... 

In its original form, the Michael addition consisted on the addition of diethyl malonate across the double bond of ethyl cinnamate in the presence of sodium ethoxide to afford a substituted pentanedioic acid ester. Currently, all reactions that involve a 1,4-addition of stabilized carbon nucleophiles to activated 7i-systems are known as Michael additions. Among the various reactants, enolates derived from p-dicarbonyl compounds are substrates of choice due to their easy deprotonation under mild conditions. Recently, Michael addition-based MCRs emerged as highly potential methodologies for the synthesis of polysubstituted heterocycles in the five- to seven-membered series. 

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