Quaternary ammonium fluorides and difluorosilicates as nucleophilic fluorination reagents
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F24%3A00582402" target="_blank" >RIV/61388963:_____/24:00582402 - isvavai.cz</a>
Alternative codes found
RIV/60461373:22310/24:43928767
Result on the web
<a href="https://doi.org/10.1039/D3OB01875J" target="_blank" >https://doi.org/10.1039/D3OB01875J</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1039/d3ob01875j" target="_blank" >10.1039/d3ob01875j</a>
Alternative languages
Result language
angličtina
Original language name
Quaternary ammonium fluorides and difluorosilicates as nucleophilic fluorination reagents
Original language description
TBAT (tetrabutylammonium difluorotriphenylsilicate) is an excellent homogeneous nucleophilic fluorination reagent, but a high excess of the reagent was reported to be essential. We hence optimized the reaction conditions and compared its nucleophilic fluorination reactivity with that of other common commercial nucleophilic fluorination reagents, such as anhydrous TBAF and TASF (tris(dimethylamino)sulfonium difluorotrimethylsilicate). As the substrates, we employed a standard set of primary and secondary octyl substrates under identical conditions. To eliminate the possibility of hydrogen fluoride elimination in the above reagents, we prepared four quaternary ammonium fluorides lacking beta-elimination possibility in the hydrocarbon chain, transformed them to the corresponding difluorotriphenylsilicates, and compared their reactivity with that of the commercial reagents. Furthermore, attempts to isolate analogous tetrabutylammonium difluoromethyldiphenylsilicate or difluorodimethylphenylsilicate failed, as was confirmed by comparison of the published experimental data with computed 19F NMR spectra. Finally, we studied the transition states of decomposition of various tetramethylammonium methylphenyldifluorosilicates by DFT methods and found that their relative energies increase with an increasing number of phenyl groups. The formation of difluorosilicates is a nearly barrierless process.
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
10406 - Analytical chemistry
Result continuities
Project
<a href="/en/project/GF21-29531K" target="_blank" >GF21-29531K: Advanced reagents for (asymmetric) nucleophilic fluorination</a><br>
Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2024
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Organic & Biomolecular Chemistry
ISSN
1477-0520
e-ISSN
1477-0539
Volume of the periodical
22
Issue of the periodical within the volume
5
Country of publishing house
GB - UNITED KINGDOM
Number of pages
10
Pages from-to
1047-1056
UT code for WoS article
001139117500001
EID of the result in the Scopus database
2-s2.0-85182388126