A Novel Approach to the Synthesis of Symmetric Optically Active 2,5-Dioxopiperazines

Basiuk, Vladimir A.; Gromovoy, Taras Yu.; Chuiko, A. A.; Soloshonok, Vadim A.; Kukhar, V. P.

doi:10.1055/s-1992-26131

Cited by 64 publications

(28 citation statements)

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“…35 Additional calculations have shown that the formation of such a compound is very unfavorable thermodynamically (endothermic by around 200 kJ/mol). Finally, although it is well-known that many amino acids easily dimerise on the surface of silica to yield substituted diketopiperazines, 36 this does not happen in our conditions, although it is quite likely that further thermal activation could promote dimerisation.…”

Section: Discussionmentioning

confidence: 82%

Theoretical and Experimental Study of the Adsorption of Neutral Glycine on Silica from the Gas Phase

Lomenech¹,

Bery²,

Costa³

et al. 2005

ChemPhysChem

115

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The adsorption of neutral glycine onto amorphous silica was investigated both theoretically and experimentally. DFT calculations were performed at the BLYP-631++G** level using a cluster approach. Several possible configurations involving the formation of H-bonds between glycine and one, two or three silanols, (SiOH) were considered. The most favorable bonding of glycine with one silanol (45 kJ/mol) occurs through the COOH moiety, forming a cycle in which the CO group is H-bond acceptor whereas the acidic OH group is H-bond donor. With two or three silanols, additional H-bonds are formed between the amine moiety and the silanols, leading to an increased adsorption energy (70 and 80 kJ/mol for two and three silanols respectively). Calculated ν CO , δ HNH and δ ΗCH are sensitive to the adsorption mode. A bathochromic shift of νCO as compared to νCO of free glycine (calculated in the 1755-1790 cm -1 range) is found for glycine in interaction with silanol(s). The more H-bonds of COOH with silanol groups, the higher the bathochromic shift. For δHNH, no shift is found for glycine adsorbed on one and two silanols (where the amine is either not bound or H bond donor), whereas a bathochromic shift is calculated with three silanols when the amine moiety is H-bond acceptor.Experimental FTIR spectra performed at RT for glycine adsorbed at 160°C on Aerosil amorphous silica exhibit bands at 1371, 1423, 1630 and 1699 cm -1 . The experimental/calculated frequencies have their best correspondance for glycine adsorbed on two silanols. It is important to note that the forms giving the best correspondence to experimental frequencies are the most stable ones. TITLE RUNNING HEAD : Adsorption of Glycine on Silica

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Section: Discussionmentioning

confidence: 82%

Theoretical and Experimental Study of the Adsorption of Neutral Glycine on Silica from the Gas Phase

Lomenech¹,

Bery²,

Costa³

et al. 2005

ChemPhysChem

115

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“…Clay minerals promote the polymerization of activated amino acid adenylates (PaechtHorowitz 1977(PaechtHorowitz , 1978Paecht-Horowitz and Eirich 1988;Paecht-Horowitz and Lahav 1977;Paecht-Horowitz et al 1970). At temperatures above the boiling point of water, polymerization of amino acids on silica or alumina was also observed without activation (Rohlfing and McAlhaney 1976;Basiuk et al 1990Basiuk et al , 1991Basiuk et al , 1992Gromovoy et al 1991;Basiuk 1992;Basiuk and Gromovoy 1994).…”

Section: Introductionmentioning

confidence: 99%

Silica, Alumina, and Clay-Catalyzed Alanine Peptide Bond Formation

Bujdák

Rode

1997

J Mol Evol

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The peptide bond formation of alanine (ala), ala + glycine (gly), ala + diglycine (gly 2 ), and ala + gly cyclic anhydride (cyc-gly 2 ) in drying/wetting cycles at 80°C was studied. Silica, alumina, and representative smectites-montmorillonite and hectorite-were used as catalysts, and the dependence of reaction yields on the available amount of water in the reaction systems was evaluated. Silica and alumina catalyze the formation of oligopeptide mainly in temperature fluctuation experiments, whereas higher amounts of water in the reaction system support clay-catalyzed reactions. Silica and alumina are much more efficient for amino acid dimerization than clays. Whereas only 0.1% of ala oligomerized on hectorite and no reaction proceeded on montmorillonite, about 0.9 and 3.8% alanine converted into its dimer and cyclic anhydride on silica and alumina, respectively. Clay minerals, on the other hand, seem to more efficiently catalyze peptide chain elongation than amino acid dimerization. The reaction yields of ala-gly-gly and glygly-ala from ala + gly 2 and ala + cyc-gly 2 reached about 0.3% on montmorillonite and 1.0% on hectorite. The possible mechanisms of these reactions and the relevance of the results for prebiotic chemistry are discussed.

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“…In principle, dehydrogenative coupling of b-amino alcohols can lead to formation of both cyclic and linear peptides (Scheme 4). Heating a 1,4-dioxane solution containing (S)-(+)-2-amino-1-propanol (2 mmol) and 1 (1 mol %) to reflux for 19 h in argon atmosphere resulted in 90 % conversion of the amino alcohol, as determined by GC-MS. Solvent evaporation, dilution of the residue with CH 2 Cl 2 , separation of an insoluble solid by filtration, and drying under vacuum gave 72 % poly(alanine) 6 (R = Me in Scheme 4) containing a minor quantity of the cyclic dimer 3,6-dimethylpiperazine-2,5-dione 7 a [21] (R = Me in Scheme 4, Table 1, entry 1). The products were characterized by NMR spectroscopy and mass spectrometry.…”

mentioning

confidence: 99%

Synthesis of Peptides and Pyrazines from β‐Amino Alcohols through Extrusion of H₂ Catalyzed by Ruthenium Pincer Complexes: Ligand‐Controlled Selectivity

et al. 2011

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A Novel Approach to the Synthesis of Symmetric Optically Active 2,5-Dioxopiperazines

Cited by 64 publications

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Theoretical and Experimental Study of the Adsorption of Neutral Glycine on Silica from the Gas Phase

Theoretical and Experimental Study of the Adsorption of Neutral Glycine on Silica from the Gas Phase

Silica, Alumina, and Clay-Catalyzed Alanine Peptide Bond Formation

Synthesis of Peptides and Pyrazines from β‐Amino Alcohols through Extrusion of H₂ Catalyzed by Ruthenium Pincer Complexes: Ligand‐Controlled Selectivity

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A Novel Approach to the Synthesis of Symmetric Optically Active 2,5-Dioxopiperazines

Cited by 64 publications

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Theoretical and Experimental Study of the Adsorption of Neutral Glycine on Silica from the Gas Phase

Theoretical and Experimental Study of the Adsorption of Neutral Glycine on Silica from the Gas Phase

Silica, Alumina, and Clay-Catalyzed Alanine Peptide Bond Formation

Synthesis of Peptides and Pyrazines from β‐Amino Alcohols through Extrusion of H2 Catalyzed by Ruthenium Pincer Complexes: Ligand‐Controlled Selectivity

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Synthesis of Peptides and Pyrazines from β‐Amino Alcohols through Extrusion of H₂ Catalyzed by Ruthenium Pincer Complexes: Ligand‐Controlled Selectivity