Synthesis of Alkyl 2-(1-t-Butylperoxyalkyl)propenoates and Ethyl 2-t-Butylperoxymethylbut-2-enoate

Navarro, C.; Degueil-Castaing, Marie; Colombani, Daniel; Maillard, B.

doi:10.1080/00397919308013300

Cited by 25 publications

(3 citation statements)

References 11 publications

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“…Brominated substrate 7 was treated with t-butyl peroxide, using KOH as base in the presence of phase-transfer catalyst benzyltriethylammonium chloride to generate mixed peroxide 8. 22 Reaction of peroxide 8 with hydroxyurea and potassium t-butoxide gave 9, the ethyl ester of the desired product. 23 In this reaction, the hydroxyl group of hydroxyurea adds to the substrate in a 1,4-Michael fashion, and the subsequent enolate eliminates t-butoxide.…”

Section: Inhibition Of Dcsc Activitymentioning

confidence: 99%

Characterization of DcsC, a PLP-independent racemase involved in the biosynthesis of d-cycloserine

2012

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The biosynthetic gene cluster responsible for the generation of the antibiotic D-cycloserine (DCS) has recently been disclosed. One of the putative enzymes described was DcsC, which showed a high degree of homology to diaminopimelate epimerase (DapF). Based on this homology, the activity of DcsC was presumed to be the racemization of O-ureido-L-serine, a proposed intermediate in DCS biosynthesis. Here we describe the cloning, overexpression and characterization of this enzyme. Using synthetic standards we show that DcsC is a racemase that operates on both O-ureido-L- and D-serine, and that it employs a two-base mechanism, with a thiolate-thiol pair in the active site. The activity of this enzyme was shown to be optimal at pH ~ 7.8, with a similar k(cat)/K(M) ratio in both the L→D direction and D→L direction. Activity was abolished with thiol-inactivating reagents such as iodoacetamide and Hg(2+) ions. Further evidence for a thiolate in the active site was obtained through the use of an epoxide-containing substrate analogue (6), which became covalently attached to the enzyme.

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Section: Inhibition Of Dcsc Activitymentioning

confidence: 99%

Characterization of DcsC, a PLP-independent racemase involved in the biosynthesis of d-cycloserine

2012

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“…Several groups have shown that allylic acetates derived from 3 undergo S N 2‘-type reactions in the absence of transition metal catalysts when nucleophiles such as β-dicarbonyl compounds, nitroalkanes,5b O -methyl ( S )-prop-2-ynyl dithiocarbonate, tert -butyl hydroperoxide, phenol, silylenol ethers in the presence of TiCl 4 , Grignard reagents, hydride, triethyl phosphite, allylic sulfones, oxosulfonium ylides, azide 15b orfor our study most relevantamines 15 are employed.…”

Section: Introductionmentioning

confidence: 99%

Combinatorial Liquid-Phase Synthesis of [1,4]Oxazepine-7-ones via the Baylis−Hillman Reaction

2000

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A new method for the synthesis of [1,4]oxazepin-7-ones from readily available aldehydes and alpha-amino alcohols was developed using the Baylis-Hillman reaction as the key step. To determine the scope and limitations of the method, a mixture library was synthesized from six aldehydes and six alpha-amino alcohols on the soluble polymer support poly(ethylene glycol) 5000 monomethyl ether (MeOPEG) via split synthesis and analyzed by GC-EIMS. Those oxazepines that were formed predominantly were resynthesized in a parallel synthesis and fully characterized. Thus, we have shown that split synthesis on MeOPEG can be an efficient method to rapidly screen the substrate spectrum of a newly developed reaction sequence.

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“…Indeed, the Michael addition 10 of 2 CH(CO 2 Et) 2 to ethyl acrylate suggested a possible addition of this carbanion to the unsaturation of 1. The formation of an epoxy peroxide as a by-product in the synthesis of 1 11 has to be considered as a good argument in favor of the feasibility of the intramolecular attack of the O-O bond, even if Yang and Finnegan 12 identified the adduct peroxide in the addition of Bu t OOH to ethyl acrylate under basic conditions. The capacity of the tert-butoxide anion to abstract a proton from malonate would make this anionic-induced decomposition a chain process.…”

mentioning

confidence: 99%

Anionically induced decomposition of 2-ethoxycarbonylprop-2-enyl peroxides

Cramay¹,

Ferdinando²,

Degueil-Castaing³

et al. 1998

Chem. Commun.

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Synthesis of Alkyl 2-(1-t-Butylperoxyalkyl)propenoates and Ethyl 2-t-Butylperoxymethylbut-2-enoate

Cited by 25 publications

References 11 publications

Characterization of DcsC, a PLP-independent racemase involved in the biosynthesis of d-cycloserine

Characterization of DcsC, a PLP-independent racemase involved in the biosynthesis of d-cycloserine

Combinatorial Liquid-Phase Synthesis of [1,4]Oxazepine-7-ones via the Baylis−Hillman Reaction

Anionically induced decomposition of 2-ethoxycarbonylprop-2-enyl peroxides

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