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Synlett 2009(1): 9-22  
DOI: 10.1055/s-0028-1087478
ACCOUNT
© Georg Thieme Verlag Stuttgart ˙ New York

The Stability/Reactivity Effects of Trifluoromethyl and Perfluoroalkyl Chains in a Masked 1,3-Dicarbonyl Derivative: The Case of 1-Acetoxy-1-iodo-2-(perfluoroalkyl)ethanes

Salem El Kharrat, Philippe Laurent*, Hubert Blancou
Institut des Biomolécules Max Mousseron, UMR-CNRS 5247 M.F.S.A., Université Montpellier 2, CC 1706, Place Eugène Bataillon, 34095 Montpellier Cedex 5, France
Fax: +33(4)67631046; e-Mail: philippe.laurent@univ-montp2.fr;
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Publication History

Received 22 May 2008
Publication Date:
12 December 2008 (online)

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Abstract

The development of an efficient and general trifluoro­methylation or perfluoroalkylation method is a major challenge in organic chemistry. This Account presents the breakthrough realized in this field using polyfluoroalkylated gem-iodoacetoxy derivatives which are useful synthons for the short preparation of various fluorinated organic compounds. The main body of this Account highlights several applications of these new derivatives as starting blocks for diverse regiospecific syntheses of trifluoromethyl- and perfluoroalkyl-containing heterocyclic compounds. A brief discussion of the use of a new method for the determination of the configuration and conformation of push-pull perfluoroalkyl-containing olefinic derivatives using coupling constant 4 J CF is included.

1 Introduction

2 Synthesis of α-Iodoalkyl Esters, R²R³C(I)OCOR¹

3 Reactivity of Polyfluoroalkylated gem-Iodoacetoxy Derivatives

3.1 Synthesis of 2-(Perfluoroalkyl)ethanals

3.2 Chemoselective Reactions

3.3 Reactivity Towards Nitrogen Compounds

3.4 Reactivity Towards Phenol Derivatives

3.5 Determination of the Stereochemistry of Push-Pull Derivatives Using a Through-Space Coupling Constant: 4 J CF

4 Summary and Outlook

Key words

aldehydes - fluorine - stereoselective synthesis - stereo­chemistry - heterocyclic compounds

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22

Laurent, P.; Biancou, H., unpublished results.