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Synthesis 2003(2): 0185-0194
DOI: 10.1055/s-2003-36812
REVIEW
© Georg Thieme Verlag Stuttgart · New York

Some Recent Results in Nucleophilic Trifluoromethylation and Introduction of Fluorinated Moieties

Bernard R. Langlois*, Thierry Billard
Université Claude Bernard-Lyon I, Laboratoire SERCOF (UMR CNRS 5622), Bâtiment Chevreul, 43 Bd du 11 Novembre 1918, 69622 Villeurbanne cedex, France
Fax: +33(4)72431323; e-Mail: Bernard.Langlois@univ-lyon1.fr;
Further Information

Publication History

Received 14 November 2002
Publication Date:
22 January 2003 (online)

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Abstract

Apart from the use of (trifluoromethyl)trimethylsilane, the scope of which has been broadened to the synthesis of tri­fluoromethyl sulfides, especially those that are bio-active, new and mild processes for the nucleophilic trifluoromethylation of non-enolizable carbonyl compounds or disulfides have been discovered from fluoroform or hemiaminals of trifluoroacetaldehyde and their derivatives. Very stable hemiaminals of fluoral (as well as their silyl ethers), readily prepared from commercially available hemiketals, have been designed as new trifluoromethylating agents. Besides their trifluoromethylating ability, they can be transformed into silyl or methyl ethers, which behave, as efficient generators of α-(tri­fluoromethyl)iminiums salts and equivalents of difluoromethylcarboxyl anions, respectively.

  • 1 Introduction

  • 2 Sulfur Trifluoromethylation with CF3SiMe3

  • 3 Trifluoromethylation with Fluoroform

  • 4 Trifluoromethylation with Stable Hemiaminals of Fluoral

  • 5 Generation and Uses of Fluoral Iminiums

  • 6 Generation and Uses of Difluorocarboxylate Anions

  • 7 Conclusion

Key words

nucleophilic trifluoromethylation - trifluoromethyl anion - fluoroform - fluoral hemiaminals - α,α-difluoromethyl esters/amides

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Work in progress, in collaboration with Prof G. Haufe (University of Münster, Germany).