Synthesis and [3,3]-sigmatropic rearrangements of 5-(pentafluorosulfanyl)-pent-3-en-2-ol, its homologues, and trifluoromethyl analogues.

The synthesis of aliphatic (pentafluoro-λ6-sulfanyl)(SF5)-substituted compounds is more challenging than that of the related CF3-substituted analogues. Previous investigations of [3,3]-sigmatropic rearrangements of γ-SF5-substituted allylic alcohols failed to yield 3-SF5-substituted carboxylic acid derivatives. Herein, we present the synthesis of a series of 1-SF5-alk-1-en-3-ols and our efforts to apply them in Johnson-Claisen, ester enolate-Claisen, and Ireland-Claisen rearrangements.

Synthesis of SF5CF2-Containing Enones and Instability of This Group in Specific Chemical Environments and Reaction Conditions.

The chemistry of the SF5CF2 moiety has been scarcely investigated. In this report, we present synthetic pathways to a variety of SF5CF2-substituted compounds starting from vinyl ethers and SF5CF2C(O)Cl. In specific chemical environments and under particular reaction conditions, the SF5CF2 moiety is unstable in downstream products resulting in the elimination of the SF5(-) anion and its decomposition to SF4 and F(-).

Ambiphilic properties of SF5CF2CF2Br derived perfluorinated radical in addition reactions across carbon-carbon double bonds.

The extraordinary properties of the pentafluorosulfanyl (SF5) group attract attention of organic chemists. While numerous SF5-substituted compounds have been synthesized, the direct introduction of SF5(CF2)n moieties has remained almost unexplored. Our investigations revealed the ambiphilic character of the SF5CF2CF2 radical.