Diethyl Fluoronitromethylphosphonate: Synthesis and Application in Nucleophilic Fluoroalkyl Additions

0429485 - ÚOCHB 2015 RIV DE eng J - Článek v odborném periodiku
Opekar, Stanislav - Pohl, Radek - Beran, Pavel - Rulíšek, Lubomír - Beier, Petr
Diethyl Fluoronitromethylphosphonate: Synthesis and Application in Nucleophilic Fluoroalkyl Additions.
Chemistry - A European Journal. Roč. 20, č. 5 (2014), s. 1453-1458. ISSN 0947-6539. E-ISSN 1521-3765
Grant CEP: GA ČR GP203/08/P310
Institucionální podpora: RVO:61388963
Klíčová slova: C1 building blocks * fluorine * nucleophilic addition * phosphanes * synthetic methods
Kód oboru RIV: CC - Organická chemie
Impakt faktor: 5.731, rok: 2014

Diethyl fluoronitromethylphosphonate (3), a previously unknown compound, was synthesized by electrophilic fluorination of diethyl nitromethylphosphonate with Selectfluor. Base-induced decomposition of 3 was studied by NMR spectroscopy, which identified diethyl fluorophosphate and fluoronitromethane as the main decomposition products. C-H acidities [pK(a) values in dimethyl sulfoxide (DMSO)] of 3, 1-fluoro-1-phenylsulfonylmethanephosphonate (1; McCarthy's reagent), tetraethyl fluoromethylenebisphosphonate (2), and some nonfluorinated phosphonates were computed, and a good correlation between calculated and experimental pK(a) values was found. The calculated C-H acidities increased in the sequence 2<1<3. Diethyl fluoronitromethylphosphonate (3) was applied in the Horner-Wadsworth-Emmons reaction with aldehydes and trifluoromethyl ketones to provide new 1-fluoro-1-nitroalkenes with good to high stereoselectivities. Alkylation of 3 was successful only with iodomethane, however, conjugate additions of 3 to Michael acceptors such as alpha,beta-unsaturated carbonyl compounds, sulfones, and nitro compounds allowed access to variously modified diethyl 1-fluoro-1-nitrophosphonates.
Trvalý link: http://hdl.handle.net/11104/0234608