Novel synthesis, reactivity, and stereochemistry of substituted 3-trifluoromethyl- and 3-perfluoroalkyl-3-phenoxyprop-2-enal

Salem El Kharrat; Philippe Laurent; Hubert Blancou

doi:10.1021/jo060764i

Novel synthesis, reactivity, and stereochemistry of substituted 3-trifluoromethyl- and 3-perfluoroalkyl-3-phenoxyprop-2-enal

J Org Chem. 2006 Sep 1;71(18):6742-52. doi: 10.1021/jo060764i.

Authors

Salem El Kharrat¹, Philippe Laurent, Hubert Blancou

Affiliation

¹ Organisation Moléculaire Evolution et Matériaux Fluorés, Université Montpellier II, Pl. E. Bataillon, 34095 Montpellier Cedex 05, France.

PMID: 16930023
DOI: 10.1021/jo060764i

Abstract

Substituted 3-phenoxy-3-perfluoroalkylprop-2-enals 3a-s are synthesized in high yields starting from a gem-iodoacetoxy derivative 1 and phenoxides 2. Then efficient syntheses of push-pull derivatives 4, 5,8a,b, and nonconjugated analogues 6 and 7 illustrate the synthetic potentialities of 3. Stereochemical studies of these perfluoroalkyl-containing trisubstituted olefinic derivatives 3-8b revealed that the (4)J(CF) coupling constant observed in the (13)C NMR spectra was crucial in the determination of their configurations and conformations in solution. The solvent polarity effect on the stereochemistry of push-pull compounds 3-5 and 8a,b was studied. Unusual significant medium polarity effect on the stereochemistry of imino enol ether derivative 4 was observed.