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Stereoselective Synthesis of Both Stereoisomers of β-Fluorostyrene Derivatives from a Common Intermediate

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Canada Research Chair in Organic and Medicinal Chemistry, Département de chimie, 1045 avenue de la Médecine, Université Laval, Québec, QC, Canada G1V 0A6
[email protected]
Cite this: Org. Lett. 2011, 13, 6, 1568–1571
Publication Date (Web):February 21, 2011
https://doi.org/10.1021/ol200302h
Copyright © 2011 American Chemical Society
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Abstract

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The stereoselective synthesis of both cis- and trans-β-fluorostyrene derivatives from a common intermediate, (Z)-1-aryl-2-fluoro-1-(trimethylsilyl)ethenes, is described. The trans isomers are obtained by a stereospecific replacement of the silyl group in the presence of water and a fluoride source, whereas the preparation of the cis isomers is achieved by a bromination/desilicobromination sequence followed by reduction of the newly created C−Br bond. A stereoselective transformation of both stereoisomers of β-fluorostyrene is also presented.

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General experimental procedures, specific details for representative reactions, and isolation and spectroscopic information for the new compounds prepared. This material is available free of charge via the Internet at http://pubs.acs.org.

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  30. Jong Hee Jeon, Ju Hee Kim, Yeo Jin Jeong, In Howa Jeong. Preparation of 2,2-difluoro-1-trialkylsilylethenylstannanes and their cross-coupling reactions. Tetrahedron Letters 2014, 55 (7) , 1292-1295. https://doi.org/10.1016/j.tetlet.2013.12.071
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  32. Tse-Lok Ho, Mary Fieser, Louis Fieser, Rick Danheiser, William Roush, Janice Smith. Lithium triethylborohydride. 2013,,, 304-304. https://doi.org/10.1002/9780471264194.fos06600.pub4
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  34. Marc-Olivier Turcotte-Savard, Jean-François Paquin. Efficient synthesis of silylated 2,2-difluorostyrene derivatives through Suzuki–Miyaura cross-coupling of 2,2-difluoro-1-iodo-1-silylethenes. Organic & Biomolecular Chemistry 2013, 11 (8) , 1367. https://doi.org/10.1039/c2ob27221k
  35. Shigeyuki Yamada. Effective Synthesis of Fluorinated Alkenes by Employing Fluorinated Vinylmetal Species. Journal of Synthetic Organic Chemistry, Japan 2013, 71 (9) , 900-911. https://doi.org/10.5059/yukigoseikyokaishi.71.900
  36. Bianca Malo-Forest, Jessye-Ann Roy, Jean-François Paquin. Bromination/desilicobromination of silylated monofluoroalkenes using tetrabutylammonium tribromide under microwave conditions. Journal of Fluorine Chemistry 2013, 145 , 77-80. https://doi.org/10.1016/j.jfluchem.2012.10.008
  37. Maxime Bergeron, Thomas Johnson, Jean-François Paquin. The Use of Fluoride as a Leaving Group: SN2′ Displacement of a CF Bond on 3,3-Difluoropropenes with Organolithium Reagents To Give Direct Access to Monofluoroalkenes. Angewandte Chemie 2011, 123 (47) , 11308-11312. https://doi.org/10.1002/ange.201105138
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  40. Grégory Landelle, Maxime Bergeron, Marc-Olivier Turcotte-Savard, Jean-François Paquin. Synthetic approaches to monofluoroalkenes. Chemical Society Reviews 2011, 40 (5) , 2867. https://doi.org/10.1039/c0cs00201a

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