Revisiting Amadori and Heyns synthesis: Critical percentage of acyclic form play the trick in addition to catalyst

Chanda, Debasree; Harohally, Nanishankar V.

doi:10.1016/j.tetlet.2018.06.050

Cited by 12 publications

(18 citation statements)

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“…[4] Similarly D-fructose with the acyclic ratio of 0.5 is best suited for demonstration of Lewis-acid mediated catalytic Heyns rearrangement reaction. [4] Our work started with primary interest to find a good Lewis acid catalyst for the synthesis of Amadori and Heyns dipeptides. Kolka et al have reported the application of Lewis acid catalysts for the synthesis of Amadori compounds derived from simple aromatic amines.…”

Section: Resultsmentioning

confidence: 99%

“…[4] Subsequently, based on this discovery, we derived several Amadori and Heyns compounds by employing inexpensive Lewis acid catalyst zinc acetate and using a substantial number of amino acids with reducing sugars. [4] One of the curios and important challenge was the application of Lewis acidcatalyzed Amadori and Heyns reactions for the synthesis of glycopeptides. Significant efforts have been made for the application of Amadori and Heyns rearrangement reactions for the synthesis of glycopeptides.…”

Section: Introductionmentioning

confidence: 99%

“…In addition, the great danger of these rearrangements is the degradation of products via the Maillard reaction cascade. However, it is possible to overcome the limitations of these rearrangement reactions by the selection of careful reaction conditions and Lewis acid catalysts [2–4] . We explored these aspects in a recent research effort and discovered that; acyclic ratio plays a critical role in the catalytic version of Amadori and Heyns synthesis [4] .…”

Section: Introductionmentioning

confidence: 99%

“…However, it is possible to overcome the limitations of these rearrangement reactions by the selection of careful reaction conditions and Lewis acid catalysts [2–4] . We explored these aspects in a recent research effort and discovered that; acyclic ratio plays a critical role in the catalytic version of Amadori and Heyns synthesis [4] . Subsequently, based on this discovery, we derived several Amadori and Heyns compounds by employing inexpensive Lewis acid catalyst zinc acetate and using a substantial number of amino acids with reducing sugars [4] .…”

Section: Introductionmentioning

confidence: 99%

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Lewis‐Acid‐Catalyzed Synthesis of Amadori and Heyns Dipeptides

2020

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Amadori and Heyns reactions are milestone reactions of carbohydrate chemistry. There have been little efforts in transforming these rearrangement reactions to useful catalytic tools. We demonstrate herein, synthesis of Amadori and Heyns dipeptides via Lewis acid-catalysis. The accomplished catalytic Amadori and Heyns synthesis is devoid of protection and deprotection steps either for dipeptides or for reducing sugar. By the developed catalytic method we achieved, tagatose Amadori dipeptides via reaction of D-galactose with dipeptides including L-alanyl glycine, L-alanyl-L-alanine, L-alanyl-L-glutamine, glycyl-L-phenylalanine, L-leucyl glycine, L-pheynylalanyl-L-valine in excellent yield. In addition, Heyns dipeptides were also achieved by employing D-fructose and dipeptides consisting of L-alanyl glycine, L-alanyl-L-alanine, L-alanyl-L-glutamine, glycyl-L-phenylalanine, L-leucyl glycine. The realized Lewis acid mediated catalytic method is practical, quantitative, and avoids chromatographic separation techniques.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Lewis‐Acid‐Catalyzed Synthesis of Amadori and Heyns Dipeptides

2020

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“…Although the synthesis and characterization of many fructosylated amino acids and peptides have been reported in literature, the majority study kinetics of their formation, specific analytical data, or the reported synthetic approaches lead to unsatisfying yields or purities [13][14][15][16][17]. Only few information about their isolation in good yields and purities has been reported, using either protected sugars as presented by the groups of Hoffmann and Horvat [18][19][20] or zinc halide catalysts as by the groups of Harohally and Norin [21][22][23]. The synthetic approach that mimics the natural reaction of free Glc with a primary amine of a protein occurring in the organism is currently still widely used by working groups studying Amadori compounds or developing HbA 1c assays [24][25][26][27][28].…”

Section: Introductionmentioning

confidence: 99%

Direct glucosone-based synthesis and HILIC-ESI-MS/MS characterization of N-terminal fructosylated valine and valylhistidine for validation of enzymatic HbA1c assays in the diagnosis of diabetes mellitus

Gerke

Buchholz

Müller³

et al. 2019

Anal Bioanal Chem

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Naturally occurring fructosamines are of high clinical significance due to their potential use in diabetes mellitus monitoring (quantification of fructosylated hemoglobin, HbA 1c ) or for the investigation of their reactivity in consecutive reactions and harmfulness towards the organism. Here we report the specific synthesis of the fructosylated dipeptide L-valyl-L-histidine (Fru-Val-His) and fructosylated L-valine (Fru-Val). Both are basic tools for the development and validation of enzymatic HbA 1c assays. The two fructosamine derivatives were synthesized via a protected glucosone intermediate which was coupled to the primary amine of Val or Val-His, performing a reductive amination reaction. Overall yields starting from fructose were 36% and 34% for Fru-Val and Fru-Val-His, respectively. Both compounds were achieved in purities > 90%. A HILIC-ESI-MS/MS method was developed for routine analysis of the synthesized fructosamines, including starting materials and intermediates. The presented method provides a well-defined and efficient synthesis protocol with purification steps and characterization of the desired products. The functionality of the fructosylated dipeptide has been thoroughly tested in an enzymatic HbA 1c assay, showing its concentration-dependent oxidative degradation by fructosyl-peptide oxidases (FPOX).

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Glycation of N-ε-carboxymethyllysine

Hellwig

Nitschke

Henle

2021

Eur Food Res Technol

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The Maillard reaction is traditionally subdivided into three stages that start consecutively and run in parallel. Here, we show that N-ε-carboxymethyllysine (CML), a compound formed in the late stage of the reaction, can undergo a second glycation event at its secondary amino group leading to a new class of Amadori rearrangement products. When N-α-hippuryl-CML was incubated in the presence of reducing sugars such as glucose, galactose, ribose, xylose, maltose, or lactose in solution for 1 h at 75 °C, the compound was degraded by 6–21%, and N-ε-carboxymethyl-N-ε-deoxyketosyl lysine derivatives were formed. Under the same conditions, lysine was 5–10 times more reactive than CML. N-α-hippuryl-N-ε-carboxymethyl-N-ε-(1-deoxyfructosyl)-l-lysine (hippuryl-CMFL) and N-ε-carboxymethyl-N-ε-(1-deoxyfructosyl)-l-lysine (CMFL) were synthesized, isolated and characterized by MS/MS and NMR experiments. Depending on the reaction conditions, up to 21% of CMFL can be converted to the furosine analogue N-ε-carboxymethyl-N-ε-furoylmethyl-l-lysine (CM-Fur) during standard acid protein hydrolysis with hydrochloric acid. Incubation of bovine serum albumin (BSA) with glucose for up to 9 weeks at 37 °C revealed the formation of CMFL in the protein as assessed by HPLC–MS/MS in the MRM mode. Under these conditions, ca. 13% of lysine residues had been converted to fructosyllysine, and 0.03% had been converted to CMFL. The detection of glycation products of glycated amino acids (heterogeneous multiple glycation) reveals a novel pathway in the Maillard reaction.

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Revisiting Amadori and Heyns synthesis: Critical percentage of acyclic form play the trick in addition to catalyst

Cited by 12 publications

References 12 publications

Lewis‐Acid‐Catalyzed Synthesis of Amadori and Heyns Dipeptides

Lewis‐Acid‐Catalyzed Synthesis of Amadori and Heyns Dipeptides

Direct glucosone-based synthesis and HILIC-ESI-MS/MS characterization of N-terminal fructosylated valine and valylhistidine for validation of enzymatic HbA1c assays in the diagnosis of diabetes mellitus

Glycation of N-ε-carboxymethyllysine

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