Diastereodivergent synthesis of 2,5-diketopiperazine derivatives of β-carboline and isoquinoline from l-amino acids

Siwicka, Aleksandra; Wojtasiewicz, Krystyna; Rosiek, Beata; Leniewski, Andrzej; Maurin, Jan K.; Czarnocki, Zbigniew

doi:10.1016/j.tetasy.2005.01.009

Cited by 23 publications

(14 citation statements)

References 50 publications

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“…Multiplying Eqns (9), (10), (11), (12) and (13) by a factor of 10 and Eqns (14), (15), (16), (17) and (18) by a factor of five and Eqn (19) by a factor of two, and then summing them with each other results in the overall reaction with the stoichiometry satisfied. In agreement with the above scheme, assuming the steadystate approximation for X þ 1 , the rate equation obtained for the non-catalysed process is Oxidative catalytic condensation of sarcosine to a diketopiperazine 21…”

Section: Reaction Mechanism For the Non-catalysed Processmentioning

confidence: 99%

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Kinetics and Mechanism of the Permanganate-Induced Oxidative Catalytic Condensation of Sarcosine to a Diketopiperazine

Khatti

Davari

Bahrami

et al. 2010

Progress in Reaction Kinetics and Mechanism

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The kinetics and mechanism of the permanganate-induced oxidative catalytic condensation reaction of sarcosine, as a secondary amino acid, in buffered medium (pH ¼ 1 -3) has been investigated spectrophotometrically. Analysis of the reaction products has shown that, in contrast to oxidation product of primary a-amino acids which is an aldehyde species, a valuable diketopiperazine compound namely 1,4-dimethylpiperazine-2,5-dione has been obtained as the sole product in 95% yield via a cheap, simple, efficient, and novel method. In an analogy to some a-amino acids in concentrated acidic medium, conclusive evidence has demonstrated delayed autocatalytic activity by Mn 2 þ in this reaction. It has been found that such activity can appear when a certain concentration ratio of Mn 2 þ to sarcosine is built up in the medium, which we call the ''critical ratio''. Decisive results have shown that the magnitude of the latter ratio depends on pH, and the exhibition of autocatalytic activity is affected by the pH and ionic strength of the medium. Regarding the ''delayed autocatalytic behaviour'' of Mn 2 þ ions, rate equations have been presented confirming observations for both catalytic and non-catalytic routes. The reaction displays a first order dependence on permanganate ions and sarcosine concentrations, both in the catalytic and non-catalytic pathways, and an apparent first order dependence on Mn 2 þ ions in the catalytic pathway. The ''critical ratio'' and ''delayed autocatalytic behaviour'' concepts have been corroborated by the correspondence of the pseudo-order rate constants of the catalytic and noncatalytic pathways to the Arrhenius and Eyring laws. The activation parameters associated with both pathways have been calculated and discussed. The much higher value of the activation entropy obtained for the catalytic process sows that this factor controls the higher reaction rate relative to that of the noncatalytic pathway. Mechanisms for both catalytic and non-catalytic routes have been proposed which include formation of a bislactam product through a diacylperoxide intermediate.

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Section: Reaction Mechanism For the Non-catalysed Processmentioning

confidence: 99%

“…Again, multiplying Eqns (9), (10), (22), (23) and (13), by a factor of 10 and Eqns (14), (15), (16), (17) and (18) by a factor of five and Eqn (19) by a factor of two, and then summing them up with each other results in the overall equation of reaction with the correct stoichiometry.…”

Section: Reaction Mechanism For the Catalysed Processmentioning

confidence: 99%

Kinetics and Mechanism of the Permanganate-Induced Oxidative Catalytic Condensation of Sarcosine to a Diketopiperazine

Khatti

Davari

Bahrami

et al. 2010

Progress in Reaction Kinetics and Mechanism

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“…Recently, we proposed a general method for the construction of isoquinoline and β-carboline systems, which utilized natural amino acids as the source of chirality [23][24][25].…”

Section: L-amino Acids As Chiral Inductors In Stereoselective Synthesmentioning

confidence: 99%

Variety of natural products derived from tryptophan and stereoselective synthesis of tetrahydro-β-carboline derivatives of pharmacological importance

Roszkowski

Czarnocki

Maurin

et al. 2007

International Congress Series

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“…The inversion of dr for proline-based substrates compared to other amino acids was previously reported for the 2,5-diketopiperazine system. 11,12 Finally, the addition performed on seven-membered rings 5k and 5l led to the corresponding hemiaminals 6k and 6l in still good yields (62 and 55%, respectively) but with a lower dr (37 : 63), likely due to greater flexibility of the seven-membered ring. 13 As aforementioned for 6h and 6j, the X-ray diffraction analysis of 6l revealed that the major isomer was the C9-C2 cis-isomer.…”

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confidence: 95%

Diastereoselective synthesis of novel aza-diketopiperazines via a domino cyclohydrocarbonylation/addition process

et al. 2014

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Herein, we report an unprecedented, short and diastereo-selective synthesis of newly reported aza-diketopiperazine (aza-DKP) scaffolds starting from amino acids. The strategy is based on a Rh(I)-catalyzed hydroformylative cyclohydrocarbonylation of allyl-substituted aza-DKP, followed by a diastereoselective functionalization of the platform. This methodology allows the synthesis of novel bicyclic and tricyclic aza-DKP scaffolds incorporating six- or seven-membered rings, with potential applications in medicinal chemistry.

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Diastereodivergent synthesis of 2,5-diketopiperazine derivatives of β-carboline and isoquinoline from l-amino acids

Cited by 23 publications

References 50 publications

Kinetics and Mechanism of the Permanganate-Induced Oxidative Catalytic Condensation of Sarcosine to a Diketopiperazine

Kinetics and Mechanism of the Permanganate-Induced Oxidative Catalytic Condensation of Sarcosine to a Diketopiperazine

Variety of natural products derived from tryptophan and stereoselective synthesis of tetrahydro-β-carboline derivatives of pharmacological importance

Diastereoselective synthesis of novel aza-diketopiperazines via a domino cyclohydrocarbonylation/addition process

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