Application of trimethylvinylsilane as a convenient synthetic precursor of (perfluoroalkyl)ethenes: An unusual fluoride-induced elimination-desilylation coupled reaction

Zoltán Szlávik, G. Tárkányi, A. Gömöry, J. Rábai

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8 Citations (Scopus)

Abstract

(equation presented) A convenient and effective method for the preparation of perfluoroalkylated ethenes is described. First, the free radical addition of perfluoroalkyl iodides to trimethylvinylsilane in the presence of AIBN gave iodoethylsilane intermediates (F(CF2)nCH2CHISiMe3, n = 4 (1), 6 (2),8 (3), 10 (4); 94-99%). Then an unusual dehydrohalogenation-desilylation reaction was effected by tetrabutylammonium fluoride, and finally the product isolation (F(CF2)nCH=CH2 (5-8), 62-87%) was facilitated using a fluorous phase separation technique. This novel approach can also be applied to adjust short C2 hydrocarbon units to functionalized fluorinated segments (e.g., HOCH2(CF2)8CH=CH2 (11), 71%). All structures were verified by state-of-the-art multinuclear one- and two-dimensional NMR experiments involving both homo-(19F-19F) and heteronuclear (1H-13C, 19F-13C) correlations based on the GMQFCOPS and inverse 1H and/or 19F detected GHSQC, GHMQC sequences with broad-band adiabatic 13C decoupling.

Original languageEnglish
Pages (from-to)2347-2349
Number of pages3
JournalOrganic Letters
Volume2
Issue number15
Publication statusPublished - Jul 27 2000

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Iodides
Hydrocarbons
Fluorides
Phase separation
decoupling
free radicals
iodides
Free Radicals
fluorides
elimination
isolation
hydrocarbons
Nuclear magnetic resonance
broadband
preparation
nuclear magnetic resonance
products
Experiments
tetrabutylammonium
azobis(isobutyronitrile)

ASJC Scopus subject areas

  • Molecular Medicine

Cite this

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title = "Application of trimethylvinylsilane as a convenient synthetic precursor of (perfluoroalkyl)ethenes: An unusual fluoride-induced elimination-desilylation coupled reaction",
abstract = "(equation presented) A convenient and effective method for the preparation of perfluoroalkylated ethenes is described. First, the free radical addition of perfluoroalkyl iodides to trimethylvinylsilane in the presence of AIBN gave iodoethylsilane intermediates (F(CF2)nCH2CHISiMe3, n = 4 (1), 6 (2),8 (3), 10 (4); 94-99{\%}). Then an unusual dehydrohalogenation-desilylation reaction was effected by tetrabutylammonium fluoride, and finally the product isolation (F(CF2)nCH=CH2 (5-8), 62-87{\%}) was facilitated using a fluorous phase separation technique. This novel approach can also be applied to adjust short C2 hydrocarbon units to functionalized fluorinated segments (e.g., HOCH2(CF2)8CH=CH2 (11), 71{\%}). All structures were verified by state-of-the-art multinuclear one- and two-dimensional NMR experiments involving both homo-(19F-19F) and heteronuclear (1H-13C, 19F-13C) correlations based on the GMQFCOPS and inverse 1H and/or 19F detected GHSQC, GHMQC sequences with broad-band adiabatic 13C decoupling.",
author = "Zolt{\'a}n Szl{\'a}vik and G. T{\'a}rk{\'a}nyi and A. G{\"o}m{\"o}ry and J. R{\'a}bai",
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TY - JOUR

T1 - Application of trimethylvinylsilane as a convenient synthetic precursor of (perfluoroalkyl)ethenes

T2 - An unusual fluoride-induced elimination-desilylation coupled reaction

AU - Szlávik, Zoltán

AU - Tárkányi, G.

AU - Gömöry, A.

AU - Rábai, J.

PY - 2000/7/27

Y1 - 2000/7/27

N2 - (equation presented) A convenient and effective method for the preparation of perfluoroalkylated ethenes is described. First, the free radical addition of perfluoroalkyl iodides to trimethylvinylsilane in the presence of AIBN gave iodoethylsilane intermediates (F(CF2)nCH2CHISiMe3, n = 4 (1), 6 (2),8 (3), 10 (4); 94-99%). Then an unusual dehydrohalogenation-desilylation reaction was effected by tetrabutylammonium fluoride, and finally the product isolation (F(CF2)nCH=CH2 (5-8), 62-87%) was facilitated using a fluorous phase separation technique. This novel approach can also be applied to adjust short C2 hydrocarbon units to functionalized fluorinated segments (e.g., HOCH2(CF2)8CH=CH2 (11), 71%). All structures were verified by state-of-the-art multinuclear one- and two-dimensional NMR experiments involving both homo-(19F-19F) and heteronuclear (1H-13C, 19F-13C) correlations based on the GMQFCOPS and inverse 1H and/or 19F detected GHSQC, GHMQC sequences with broad-band adiabatic 13C decoupling.

AB - (equation presented) A convenient and effective method for the preparation of perfluoroalkylated ethenes is described. First, the free radical addition of perfluoroalkyl iodides to trimethylvinylsilane in the presence of AIBN gave iodoethylsilane intermediates (F(CF2)nCH2CHISiMe3, n = 4 (1), 6 (2),8 (3), 10 (4); 94-99%). Then an unusual dehydrohalogenation-desilylation reaction was effected by tetrabutylammonium fluoride, and finally the product isolation (F(CF2)nCH=CH2 (5-8), 62-87%) was facilitated using a fluorous phase separation technique. This novel approach can also be applied to adjust short C2 hydrocarbon units to functionalized fluorinated segments (e.g., HOCH2(CF2)8CH=CH2 (11), 71%). All structures were verified by state-of-the-art multinuclear one- and two-dimensional NMR experiments involving both homo-(19F-19F) and heteronuclear (1H-13C, 19F-13C) correlations based on the GMQFCOPS and inverse 1H and/or 19F detected GHSQC, GHMQC sequences with broad-band adiabatic 13C decoupling.

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