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Xumu Zhang - One of the best experts on this subject based on the ideXlab platform.

Tsuneo Imamoto - One of the best experts on this subject based on the ideXlab platform.

Albert S. C. Chan - One of the best experts on this subject based on the ideXlab platform.

Luís S. Monteiro - One of the best experts on this subject based on the ideXlab platform.

  • Synthesis and preliminary biological evaluation of new phenolic and catecholic Dehydroamino Acid derivatives
    Tetrahedron, 2017
    Co-Authors: Luís S. Monteiro, Paula M. T. Ferreira, Sandra Oliveira, Fátima Paiva-martins, David M. Pereira, Paula B. Andrade, Patrícia Valentão
    Abstract:

    Abstract A library of N -phenolic and N -catecholic Dehydroamino Acid derivatives was prepared using an innovative synthetic strategy that involves mild reaction conditions and simple work-up procedures. The method comprises coupling of phenolic or catecholic Acids with β-hydroxyamino Acids followed by tert -butyloxycarbonylation of all hydroxyl groups using tert -butyldicarbonate and 4-dimethylaminopyridine as catalyst. Treatment of these amino Acids with N,N,N′,N′ -tetramethylguanidine affords the corresponding O - tert -butyloxycarbonylDehydroamino Acid derivative. Deprotection of the aromatic hydroxyl groups is carried out with trifluoroacetic Acid. This synthetic strategy can be applied in a one-pot procedure and yields compounds that can be easily inserted into peptides or other biomolecules after cleavage of the C-protecting group. Preliminary studies of cell viability show that these new compounds display very low or no toxicity. These Dehydroamino Acids with a phenolic or catecholic moiety can have intrinsic biological activity or used to prepare new hydrogels that mimic mussel adhesive proteins.

  • High yielding synthesis of N-ethyl Dehydroamino Acids
    Amino Acids, 2012
    Co-Authors: Luís S. Monteiro, Ana S. Suárez
    Abstract:

    Recently we reported the use of a sequence of alkylation and dehydration methodologies to obtain N -ethyl-α, β-Dehydroamino Acid derivatives. The application of this N-alkylation procedure to several methyl esters of β,β-dibromo and β-bromo, β-substituted Dehydroamino Acids protected with standard amine protecting groups was subsequently reported. The corresponding N -ethyl, β-bromo Dehydroamino Acid derivatives were obtained in fair to high yields and some were used as substrates in Suzuki cross-coupling reactions to give N -ethyl, β,β-disubstituted dehydroalanine derivatives. Herein, we further explore N-ethylation of β-halo Dehydroamino Acid derivatives using triethyloxonium tetrafluoroborate as alkylating agent, but substituting N,N -diisopropylethylamine for potassium tert -butoxide as auxiliary base. In these conditions, for all β-halo Dehydroamino Acid derivatives, reactions were complete and the N -ethylated derivative could be isolated in high yield. This method was also applied for N-ethylation of non-halogenated Dehydroamino Acids. Again, with all compounds the reactions were complete and the N -ethyl Dehydroamino Acid derivatives could be isolated in high yields. Some of these N -ethyl Dehydroamino Acid methyl ester derivatives were converted in high yields to their corresponding Acids and coupled to an amino Acid methyl ester to give N -ethyl dehydrodipeptide derivatives in good yields. Thus, this method constitutes a general procedure for high yielding synthesis of N -ethylated Dehydroamino Acids, which can be further applied in peptide synthesis.

  • Synthesis of Novel Nonproteinogenic Amino Acids: N-Ethyl-α,β-Dehydroamino Acid Methyl Esters
    European Journal of Organic Chemistry, 2010
    Co-Authors: Luís S. Monteiro, Joanna Kołomańska, Ana C. Suárez
    Abstract:

    Two routes for the synthesis of N-ethyl-N-(4-nitrophenyl-sulfonyl)-α,β-Dehydroamino Acid derivatives from serine, threonine and phenylserine derivatives are presented. One route consists of dehydration of N-(4-nitrophenylsulfonyl)-β-hydroxyamino Acid esters with di-tert-butyl dicarbonate catalyzed by 4-(dimethylamino)pyridine, followed by alkylation of the N-(4-nitrophenylsulfonyl)-α,β-Dehydroamino Acid methyl esters obtained with triethyloxonium tetrafluoroborate. The second strategy applied the same procedures but in inverse order: alkylation followed by dehydration. These methods made it possible to obtain for the first time, new non-natural amino Acids, which incorporate both an N-ethyl and an α,β-dehydro moiety.

  • synthesis of non proteinogenic amino Acids from n 4 toluenesulfonyl Dehydroamino Acid derivatives
    Tetrahedron Letters, 2002
    Co-Authors: Paula M. T. Ferreira, Hernâni L. S. Maia, Luís S. Monteiro
    Abstract:

    By treating N-(4-toluenesulfonyl)-N-(tert-butyloxycarbonyl)-Dehydroamino Acid derivatives with different reactants under different conditions, a variety of new amino Acids are obtained, viz. (i) α-alcoxy-α-amino Acids, (ii) α,α-diamino Acids and (iii) novel β-substituted Dehydroamino Acids.

  • michael addition of thiols carbon nucleophiles and amines to Dehydroamino Acid and dehydropeptide derivatives
    Journal of The Chemical Society-perkin Transactions 1, 2001
    Co-Authors: Paula M. T. Ferreira, Luís S. Monteiro, Hernâni L. S. Maia, Joana Sacramento
    Abstract:

    Michael additions of nitrogen heterocycles, thiols, carbon nucleophiles and amines to dehydroalanine derivatives, including a glycyldehydroalanine peptide, are performed in fair to good yields. DiDehydroaminobutyric Acid derivatives react only with the stronger nucleophiles but in considerably lower yields and often no reaction is observed with the corresponding didehydrophenylalanine derivatives. When a tosyl group is bonded to the nitrogen atom of the Dehydroamino Acid, in some cases the addition product undergoes elimination of this group and yields the corresponding β-substituted derivative of the α,β-diDehydroamino Acid. Addition of some β-dicarbonyl compounds leads to formation of products to which the structure of α,α-disubstituted cyclic amino Acid derivatives is assigned.

Matthias Beller - One of the best experts on this subject based on the ideXlab platform.

  • iridium catalyzed hydrogenation of β Dehydroamino Acid derivatives using monodentate phosphoramidites
    European Journal of Organic Chemistry, 2008
    Co-Authors: Stephan Enthaler, Giulia Erre, Kathrin Junge, Kristin Schröder, Daniele Addis, Dirk Michalik, Marko Hapke, Dmitry Redkin, Matthias Beller
    Abstract:

    The iridium-catalyzed asymmetric hydrogenation of 13 different β-Dehydroamino Acid derivatives to give optically active β-amino Acid esters has been examined. Readily accessible monodentate octahydrobinaphthol-based phosphoramidites were used as chiral ligands. Good to excellent enantioselectivities and yields were obtained for the E isomers, whereas poorer catalyst performance was found for the Z isomers. Importantly, to obtain high enantioselectivity, substitution at the 3,3′-positions of the ligands was necessary. Enantioselectivities of up to 94 % ee were achieved under optimized conditions.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

  • Iridium‐Catalyzed Hydrogenation of β‐Dehydroamino Acid Derivatives Using Monodentate Phosphoramidites
    European Journal of Organic Chemistry, 2008
    Co-Authors: Stephan Enthaler, Giulia Erre, Kathrin Junge, Kristin Schröder, Daniele Addis, Dirk Michalik, Marko Hapke, Dmitry Redkin, Matthias Beller
    Abstract:

    The iridium-catalyzed asymmetric hydrogenation of 13 different β-Dehydroamino Acid derivatives to give optically active β-amino Acid esters has been examined. Readily accessible monodentate octahydrobinaphthol-based phosphoramidites were used as chiral ligands. Good to excellent enantioselectivities and yields were obtained for the E isomers, whereas poorer catalyst performance was found for the Z isomers. Importantly, to obtain high enantioselectivity, substitution at the 3,3′-positions of the ligands was necessary. Enantioselectivities of up to 94 % ee were achieved under optimized conditions.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

  • Development of Practical Rhodium Phosphine Catalysts for the Hydrogenation of β-Dehydroamino Acid Derivatives
    Organic Process Research & Development, 2007
    Co-Authors: Stephan Enthaler, Giulia Erre, Kathrin Junge, Jens Holz, Armin Börner, Elisabetta Alberico, Ilenia Nieddu, Serafino Gladiali, Matthias Beller
    Abstract:

    The rhodium-catalyzed asymmetric hydrogenation of various β-Dehydroamino Acid derivatives to give optically active β-amino Acids has been examined. Chiral monodentate 4,5-dihydro-3H-dinaphthophosphepines, which are easily tuned and accessible in a multi-10-g scale, have been used as ligands. The enantioselectivity is largely dependent on the nature of the substituent at the phosphorous atom and on the structure of the substrate. Applying optimized conditions up to 94% ee was achieved.