Biomimetic Orthogonal Removal of Arylacyl Protecting Groups from the C-Terminus of Substituted Amino Acids and Oligopeptides via Flavin N(5)-iminium Covalent Adducts

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22310%2F25%3A43932042" target="_blank" >RIV/60461373:22310/25:43932042 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/60461373:22340/25:43932042

Výsledek na webu

<a href="https://advanced.onlinelibrary.wiley.com/doi/epdf/10.1002/adsc.202401556" target="_blank" >https://advanced.onlinelibrary.wiley.com/doi/epdf/10.1002/adsc.202401556</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/adsc.202401556" target="_blank" >10.1002/adsc.202401556</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Biomimetic Orthogonal Removal of Arylacyl Protecting Groups from the C-Terminus of Substituted Amino Acids and Oligopeptides via Flavin N(5)-iminium Covalent Adducts

Popis výsledku v původním jazyce

Flavin co-factors and other flavin derivatives are traditionally associated with one- or two-electron redox reactions. Flavins also form covalent intermediates with a variety of substrates. While extensive attention has focused on reactions at the C(4a) position of the flavin ring, recent interest has shifted toward the dynamic potential of the N(5) atom. In our study, we demonstrate the formation of artificial flavin N(5)-iminium covalent adducts via nucleophilic attack by enolates derived from arylacyl esters at the flavin N(5) position. This interaction mimics the biosynthesis of ether phospholipids catalysed by alkyl-dihydroxyacetone phosphate synthase via an N(5)-FAD iminium adduct formation and fatty acid release. Accordingly, we developed a method for the selective removal of phenacyl and 2-naphthylacetyl protecting groups from the C-terminus of α-amino acids and di- and tripeptides using biomimetic flavin organocatalysis. Although many approaches are currently available for protection of C-terminus of peptides, their removal often requires harsh conditions, which cause racemization and the loss of optical purity, together with other side reactions. Our method is versatile, mild, orthogonal to most functional and protecting groups and maintains optical purity of α-amino acids. From general point of view, the method signifies the groundbreaking application of the non-canonical reactivity of flavins in organic synthesis. © 2025 The Authors. Published by Wiley-VCH GmbH.

Název v anglickém jazyce

Biomimetic Orthogonal Removal of Arylacyl Protecting Groups from the C-Terminus of Substituted Amino Acids and Oligopeptides via Flavin N(5)-iminium Covalent Adducts

Popis výsledku anglicky

Flavin co-factors and other flavin derivatives are traditionally associated with one- or two-electron redox reactions. Flavins also form covalent intermediates with a variety of substrates. While extensive attention has focused on reactions at the C(4a) position of the flavin ring, recent interest has shifted toward the dynamic potential of the N(5) atom. In our study, we demonstrate the formation of artificial flavin N(5)-iminium covalent adducts via nucleophilic attack by enolates derived from arylacyl esters at the flavin N(5) position. This interaction mimics the biosynthesis of ether phospholipids catalysed by alkyl-dihydroxyacetone phosphate synthase via an N(5)-FAD iminium adduct formation and fatty acid release. Accordingly, we developed a method for the selective removal of phenacyl and 2-naphthylacetyl protecting groups from the C-terminus of α-amino acids and di- and tripeptides using biomimetic flavin organocatalysis. Although many approaches are currently available for protection of C-terminus of peptides, their removal often requires harsh conditions, which cause racemization and the loss of optical purity, together with other side reactions. Our method is versatile, mild, orthogonal to most functional and protecting groups and maintains optical purity of α-amino acids. From general point of view, the method signifies the groundbreaking application of the non-canonical reactivity of flavins in organic synthesis. © 2025 The Authors. Published by Wiley-VCH GmbH.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10401 - Organic chemistry

Projekt

<a href="/cs/project/GA21-14179S" target="_blank" >GA21-14179S: Nová strategie přepólování s využitím kovalentní organokatalýzy s flaviny</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2025

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

ADVANCED SYNTHESIS &amp; CATALYSIS

ISSN

1615-4150

e-ISSN

—

Svazek periodika

367

Číslo periodika v rámci svazku

9

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

9

Strana od-do

"e202401556"

Kód UT WoS článku

001419040500001

EID výsledku v databázi Scopus

2-s2.0-85217670935