Modular Synthesis of Dihydropyranones through Cyclization and Organometallic Functionalization
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61389030%3A_____%2F25%3A00643874" target="_blank" >RIV/61389030:_____/25:00643874 - isvavai.cz</a>
Alternative codes found
RIV/61989592:15310/25:73634642
Result on the web
<a href="https://doi.org/10.1002/ejoc.202500848" target="_blank" >https://doi.org/10.1002/ejoc.202500848</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1002/ejoc.202500848" target="_blank" >10.1002/ejoc.202500848</a>
Alternative languages
Result language
angličtina
Original language name
Modular Synthesis of Dihydropyranones through Cyclization and Organometallic Functionalization
Original language description
Dihydropyranones are key structural motifs in biologically active polyketides. We report a reproducible and scalable method for synthesizing 3-methoxy-4,5-dihydropyran-2-ones (MeO-DHP-2-ones) via base-promoted cyclization of hydroxy alkynes. Mechanistic and computational studies revealed that water content and reaction time critically influence lactonization efficiency. Two optimized protocols – using potassium carbonate (K2CO3) or in situ generated sodium methoxide (MeONa) – enabled consistent yields across multiple substrates. Cyclization in deuterated methanol provided deuterium-enriched DHP-2-one scaffolds with high isotopic incorporation, valuable for mechanistic and medicinal applications. The transformation of DHP-2-ones into 4,5-dihydropyran-4-ones (DHP-4-ones) was achieved via organometallic addition followed by a tailored workup involving aqueous hydrochloric acid and boron trifluoride diethyl etherate (BF3·OEt2). This protocol proved robust and scalable, compatible with both organolithium and organomagnesium reagents, although the latter afforded lower yields. Mechanistic analysis highlighted key steps including hemiacetal formation, oxonium activation, and controlled hydrolysis. The methodology enables multigram-scale preparation of both DHP-2-one and DHP-4-one scaffolds and provides a streamlined route toward spiroacetal precursors.
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
Result was created during the realization of more than one project. More information in the Projects tab.
Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
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
European Journal of Organic Chemistry
ISSN
1434-193X
e-ISSN
1099-0690
Volume of the periodical
28
Issue of the periodical within the volume
48
Country of publishing house
DE - GERMANY
Number of pages
7
Pages from-to
e202500848
UT code for WoS article
001609848800001
EID of the result in the Scopus database
2-s2.0-105021262425