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Synthesis of new β-amidodehydroaminobutyric acid derivatives and of new tyrosine derivatives using copper catalyzed C–N and C–O coupling reactions

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Abstract

Several β-amidodehydroaminobutyric acid derivatives were prepared from N,C-diprotected β-bromodehydroaminobutyric acids and amides by a copper catalyzed C–N coupling reaction. The best reaction conditions include the use of a catalytic amount of CuI, N,N′-dimethylethylenediamine as ligand and K2CO3 as base in toluene at 110 °C. The stereochemistry of the products was determined using NOE difference experiments and the results obtained are in agreement with an E-stereochemistry. Thus, the stereochemistry is maintained in the case of the E-isomers of β-bromodehydroaminobutyric acid derivatives, but when the Z-isomers were used as substrates the reaction proceeds with inversion of configuration. The use of β-bromodehydrodipeptides as substrates was also tested. It was found that the reaction outcome depend on the stereochemistry of the β-bromodehydrodipeptide and on the nature of the first amino acid residue. The products isolated were the β-amidodehydrodipeptide derivatives and/or the corresponding dihydropyrazines. The same catalytic system (CuI/N,N′-dimethylethylene diamine) was used in the C–O coupling reactions between a tyrosine derivative and aryl bromides. The new O-aryltyrosine derivatives were isolated in moderate to good yields. The photophysical properties of two of these compounds were studied in four solvents of different polarity. The results show that these compounds after deprotection can be used as fluorescence markers.

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Acknowledgments

This work was financed by FEDER through “Programa Operacional Factores de Competitividade”—COMPETE and by FCT—“Fundação para a Ciência e Tecnologia” through project “Projecto Estratégico—UI 686—2011-2012" Ref: PEst-C/QUI/UI0686/2011. The NMR spectrometer is part of the National NMR Network (RNRMN) and was purchased in the framework of the National Programme for Scientific Re-equipment, contract REDE/1517/RMN/2005, with funds from POCI 2010 (FEDER) and Fundação para a Ciência e a Tecnologia (FCT) and is supported with funds from FCT. G.P. acknowledges FCT for a PhD grant SFRH/BD/38766/2007. H.V. acknowledges FCT for a PhD grant SFRH/BD/7265/2010.

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  1. Ferreira Centro de Química, University of Minho, Gualtar, 4710-057, Braga, Portugal

    G. Pereira, H. Vilaça & P. M. T. Ferreira

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  1. G. Pereira
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  2. H. Vilaça
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  3. P. M. T. Ferreira
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Correspondence to P. M. T. Ferreira.

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Pereira, G., Vilaça, H. & Ferreira, P.M.T. Synthesis of new β-amidodehydroaminobutyric acid derivatives and of new tyrosine derivatives using copper catalyzed C–N and C–O coupling reactions. Amino Acids 44, 335–344 (2013). https://doi.org/10.1007/s00726-012-1337-4

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  • DOI: https://doi.org/10.1007/s00726-012-1337-4

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