Catalytic artificial nitroalkane oxidases - a way towards organocatalytic umpolung

Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22310%2F23%3A43926305" target="_blank" >RIV/60461373:22310/23:43926305 - isvavai.cz</a>
Alternative codes found
RIV/60461373:22810/23:43926305
Result on the web
<a href="https://pubs.rsc.org/en/content/articlepdf/2023/ob/d3ob00101f" target="_blank" >https://pubs.rsc.org/en/content/articlepdf/2023/ob/d3ob00101f</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1039/d3ob00101f" target="_blank" >10.1039/d3ob00101f</a>

Result language
angličtina
Original language name
Catalytic artificial nitroalkane oxidases - a way towards organocatalytic umpolung
Original language description
Nitroalkane oxidases (NAOs) are flavoenzymes that catalyse the oxidation of nitroalkanes to their corresponding carbonyl compounds while producing nitrite anions. Herein, we present an artificial catalytic system using flavins or ethylene-bridged flavinium salts that works via an NAO-like process. Under conditions optimised in terms of solvent, base, temperature and oxygen pressure, primary nitroalkanes were transformed to aldehydes. In our system, aldehydes immediately reacted with other nitroalkane molecules to form β-nitroalcohols. The reduced flavin catalyst was re-oxidised by oxygen. An alternative mechanism towards β-nitroalcohols via 5-(2-nitrobutyl)-1,5-dihydroflavin was suggested through quantum chemical calculations and by trapping and characterising this dihydroflavin intermediate. Interestingly, 5-(2-nitrobutyl)-1,5-dihydroflavin is an analogue of the flavin adenine dinucleotide adduct previously observed in an NAO X-ray structure. In both mechanistic pathways, flavin-5-iminium species is formed by nitroalkanide addition to flavin. This process represents flavin-based umpolung of an original donor to an acceptor. © 2023 The Royal Society of Chemistry.
Czech name
—
Czech description
—

Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
—
OECD FORD branch
10401 - Organic chemistry

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)

Publication year
2023
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Similar results(10)