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.

The development of an efficient and general trifluoro�methylation or perfluoroalkylation method is a major challenge in organic chemistry. This Account presents the breakthrough realized in this field using polyfluoroalkylated <italic>gem</italic>-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<italic>J</italic>CF is included. 1 Introduction 2 Synthesis of α-Iodoalkyl Esters, R�R�C(I)OCOR� 3 Reactivity of Polyfluoroalkylated <italic>gem</italic>-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<italic>J</italic>CF 4 Summary and Outlook [ABSTRACT FROM AUTHOR]