[3,3] Sigmatropic Rearrangement of Some Fluorinated 1,5-Hexadienes

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Title:[3,3] Sigmatropic Rearrangement of Some Fluorinated 1,5-Hexadienes
Creators:
Dolbier, William R.
Palmer, Keith W.
Tian, Feng
Fiedorow, Piotr
Zaganiaczyk, Andrzej
Koroniak, Henryk
Journal or Publication Title:
Collection of Czechoslovak Chemical Communications, 67, 10, pp. 1517-1532
Uncontrolled Keywords:Cope rearrangement, <i>Ab initio</i> calculations, Conformation analysis, Sigmatropic rearrangements, Fluorinated compounds, Transition states, Dienes

Abstract

Fluorine atoms incorporated into 1,5-hexadiene molecule should influence the kinetic as well as the thermodynamic parameters of [3,3] sigmatropic rearrangement (Cope rearrangement). Within few decades is has been documented that this transformation proceeds in a concerted manner, rather than stepwise with some radical intermediates involved. Few new terminally fluorinated 1,5-hexadienes (compounds <strong>3</strong>, <strong>5A</strong>, <strong>7</strong>, <strong>9</strong> and <strong>5B</strong>) have been synthesized. The activation parameters of rearrangement have been determined and compared with those known for hydrocarbon analogues. While systems developing chair-like transition states (compounds <strong>3</strong> and <strong>5</strong>) showed close similarity with hydrocarbon analogues (compound <strong>1</strong>), those developing boat-like transition states (compounds <strong>7</strong>, <strong>9</strong> and <strong>5B</strong>) may proceed through radical stepwise mechanism. Computational studies of the transition states were carried out, showing that only <i>ab initio</i> methods (MP2 and especially DFT) can give approximate correlation with experimental data, whereas in the case of hydrocarbon analogues even simple semiempirical methods (AM1) were reliable enough to reproduce experimental results. <p>

Title:[3,3] Sigmatropic Rearrangement of Some Fluorinated 1,5-Hexadienes
Creators:
Dolbier, William R.
Palmer, Keith W.
Tian, Feng
Fiedorow, Piotr
Zaganiaczyk, Andrzej
Koroniak, Henryk
Uncontrolled Keywords:Cope rearrangement, <i>Ab initio</i> calculations, Conformation analysis, Sigmatropic rearrangements, Fluorinated compounds, Transition states, Dienes
Divisions:Life and Chemical Sciences > Institute of Organic Chemistry and Biochemistry > Collection of Czechoslovak Chemical Communications
Journal or Publication Title:Collection of Czechoslovak Chemical Communications
Volume:67
Number:10
Page Range:pp. 1517-1532
ISSN:0010-0765
E-ISSN:1212-6950
Publisher:Institute of Organic Chemistry and Biochemistry
Related URLs:
URLURL Type
http://dx.doi.org/10.1135/cccc20021517UNSPECIFIED
ID Code:2012
Item Type:Article
Deposited On:06 Feb 2009 17:14
Last Modified:06 Feb 2009 16:14

Citation

Dolbier, William R.; Palmer, Keith W.; Tian, Feng; Fiedorow, Piotr; Zaganiaczyk, Andrzej; Koroniak, Henryk (2002) [3,3] Sigmatropic Rearrangement of Some Fluorinated 1,5-Hexadienes. Collection of Czechoslovak Chemical Communications, 67 (10). pp. 1517-1532. ISSN 0010-0765

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