Synthesis and Chemistry of α,β‐Didehydroamino Acids

Kazmaier, Uli

doi:10.1002/9783527631780.ch1

Cited by 10 publications

(9 citation statements)

References 288 publications

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“…Due to the lack of reactivity of the amino group as well as the carboxylate, dehydroamino acids have hardly employed as building blocks in peptide synthesis. Therefore, the olefinic double bond is commonly introduced after the peptide backbone is assembled and typically this is achieved by elimination when a leaving group occupies the β-position [ 2 ]. Especially peptides containing dehydroalanine as found in argyrin ( 2 ) can be prepared from a precursor that contains a selenide substituent in the β-position [ 3 ].…”

Section: Introductionmentioning

confidence: 99%

Studies on the synthesis of peptides containing dehydrovaline and dehydroisoleucine based on copper-mediated enamide formation

Gille

Kirschning

2016

Beilstein J. Org. Chem.

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SummaryThe preparation of peptide fragments containing dehydrovaline and dehydroisoleucine moieties present in the antibiotic myxovalargin is reported. Peptide formation is based on a copper-mediated C–N cross-coupling protocol between an acyl amide and a peptidic vinyl iodide. The presence of a neighboring arginine in the vinyl iodide posed a challenge with respect to the choice of the protecting group and the reaction conditions. It was found that ornithine – a suitable precursor – is better suited than arginine for achieving good yields for the C–N cross-coupling reaction. The optimized conditions were utilized for the synthesis of peptides 32, 33, 39 and 40 containing a neighboring ornithine as well as for the tripeptide 44 containing dehydroisoleucine with the correct stereochemistry.

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Section: Introductionmentioning

confidence: 99%

Studies on the synthesis of peptides containing dehydrovaline and dehydroisoleucine based on copper-mediated enamide formation

Gille

Kirschning

2016

Beilstein J. Org. Chem.

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“…α-Thio-linked glycosyl amino acids have been obtained by condensation of a β-bromoalanine derivative with the corresponding thiolate salt of the carbohydrate . On the other hand, dehydroalanine (Dha) − is an unsaturated amino acid of both biological and synthetic interest used as chemical precursor to a range of site-selective PTM by the conjugate addition of thiols . For instance, thiols with large alkyl chains or fluorescent groups, cysteine derivatives, and thioacetate are examples of nucleophiles used to install PTM on peptides by this method.…”

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confidence: 99%

Bifunctional Chiral Dehydroalanines for Peptide Coupling and Stereoselective S-Michael Addition

et al. 2016

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A second generation of chiral bicyclic dehydroalanines easily accessible from serine has been developed. These scaffolds behaved as excellent S-Michael acceptors when tri-O-acetyl-2-acetamido-2-deoxy-1-thio-α-d-galactopyranose (abbreviated as GalNAc-α-SH) was used as a nucleophile. This addition proceeds with total chemo- and stereoselectivity, complete atom economy, quickly, and at room temperature, making it a true click reaction. The Michael adducts were easily transformed into S-(2-acetamido-2-deoxy-α-d-galactopyranosyl)-l- and -d-cysteines, which can be regarded as mimics of the Tn antigen derived from l-Ser (α-d-GalNAc-l-Ser) and d-Ser (α-d-GalNAc-d-Ser), respectively.

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“…Dehydroalanine (Dha) is a unique and versatile noncanonical, yet naturally occurring, α,β-unsaturated amino acid endowed with peculiar structural properties and various reactivity profiles due to the presence of both an α,β-unsaturated ester functionality and an enamide moiety on the same carbon of the double bond . Because of the multiple functionalities of Dha, several electrophilic addition reactions onto the enamide moiety as well as various Michael additions and cycloadditions across the α,β-unsaturated carbonyl system have been demonstrated, proving its function as an important precursor to a variety of novel α-amino acids and modified peptides .…”

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confidence: 99%

Organocatalytic Aza-Friedel–Crafts/Lactonization Domino Reaction of Naphthols and Phenols with 2-Acetamidoacrylate to Naphtho- and Benzofuranones Bearing a Quaternary Center at the C3 Position

et al. 2018

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N-Acetyl ketimine generated from methyl 2-acetamidoacrylate was explored to develop an unprecedented domino aza-Friedel-Crafts/lactonization reaction with naphthols and phenols (including 5-hydroxyindoles). This novel method requires a catalyst loading of only 5 mol % of a phosphoric acid catalyst and provides a new series of 3-NHAc-naphtho- and benzofuranone derivatives bearing tetra-substituted stereogenic centers in moderate-to-good yields. The enantioselective variant using BINOL-derived phosphoric acids was also explored with 1-naphthol, providing the desired product with moderate enantioselectivities (up to 99:1 following recrystallization).

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Synthesis and Chemistry of α,β‐Didehydroamino Acids

Cited by 10 publications

References 288 publications

Studies on the synthesis of peptides containing dehydrovaline and dehydroisoleucine based on copper-mediated enamide formation

Studies on the synthesis of peptides containing dehydrovaline and dehydroisoleucine based on copper-mediated enamide formation

Bifunctional Chiral Dehydroalanines for Peptide Coupling and Stereoselective S-Michael Addition

Organocatalytic Aza-Friedel–Crafts/Lactonization Domino Reaction of Naphthols and Phenols with 2-Acetamidoacrylate to Naphtho- and Benzofuranones Bearing a Quaternary Center at the C3 Position

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