Biomimetic Orthogonal Removal of Arylacyl Protecting Groups from the C-Terminus of Substituted Amino Acids and Oligopeptides via Flavin N(5)-iminium Covalent Adducts
The result's identifiers
Result code in 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>
Alternative codes found
RIV/60461373:22340/25:43932042
Result on the web
<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>
Alternative languages
Result language
angličtina
Original language name
Biomimetic Orthogonal Removal of Arylacyl Protecting Groups from the C-Terminus of Substituted Amino Acids and Oligopeptides via Flavin N(5)-iminium Covalent Adducts
Original language description
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.
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10401 - Organic chemistry
Result continuities
Project
<a href="/en/project/GA21-14179S" target="_blank" >GA21-14179S: Novel umpolung strategy using flavin covalent organocatalysis</a><br>
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)
Others
Publication year
2025
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
ADVANCED SYNTHESIS & CATALYSIS
ISSN
1615-4150
e-ISSN
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Volume of the periodical
367
Issue of the periodical within the volume
9
Country of publishing house
DE - GERMANY
Number of pages
9
Pages from-to
"e202401556"
UT code for WoS article
001419040500001
EID of the result in the Scopus database
2-s2.0-85217670935