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

Piotr Dudziński; Andrej V Matsnev; Joseph S Thrasher; Günter Haufe

doi:10.1021/acs.joc.6b00550

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

J Org Chem. 2016 Jun 3;81(11):4454-63. doi: 10.1021/acs.joc.6b00550. Epub 2016 May 16.

Authors

Piotr Dudziński^{1

2}, Andrej V Matsnev³, Joseph S Thrasher³, Günter Haufe¹

Affiliations

¹ Organisch-Chemisches Institut, Westfälische Wilhelms-Universität Münster , Corrensstrasse 40, D-48149 Münster, Germany.
² International Graduate School of Chemistry, University of Münster , Wilhelm-Klemm-Strasse 10, D-48149 Münster, Germany.
³ Department of Chemistry, Advanced Materials Research Laboratory, Clemson University , 91 Technology Drive, Anderson, South Carolina 29625, United States.

PMID: 27159371
DOI: 10.1021/acs.joc.6b00550

Abstract

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(-). Surprisingly, the formed F(-) can attack the intermediate difluorovinyl moiety to form trifluoromethyl substituted products. This appears to happen when an intermediate neighboring group participation involving a double bond is possible. Under slightly different conditions, the reaction stops at the stage of a difluorovinyl compound.

Publication types

Research Support, Non-U.S. Gov't
Research Support, U.S. Gov't, Non-P.H.S.