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Synthesis of #-(Pentafluorosulfanyl)- and #-(Trifluoromethyl)-substituted Carboxylic Acid Derivatives by Ireland-Claisen Rearrangement Anna-Lena Dreier, Bernd Beutel, Christian Mück-Lichtenfeld, Andrej V Matsnev, Joseph S. Thrasher, and Günter Haufe J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.6b02805 • Publication Date (Web): 30 Dec 2016 Downloaded from http://pubs.acs.org on December 30, 2016
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The Journal of Organic Chemistry
Synthesis of α-(Pentafluorosulfanyl)- and α-(Trifluoromethyl)-substituted Carboxylic Acid Derivatives by Ireland-Claisen Rearrangement Anna-Lena Dreier,† Bernd Beutel,† Christian Mück-Lichtenfeld,† Andrej V. Matsnev,‡ Joseph S. Thrasher,‡ and Günter Haufe *,†,§ †
Organisch-Chemisches Institut, Universität Münster, Corrensstraße 40, 48149 Münster,
Germany ‡
Department of Chemistry, Advanced Materials Research Laboratory, Clemson University,
91 Technology Drive, Anderson, South Carolina 29625, United States of America §
Cells-in-Motion Cluster of Excellence, Universität Münster, Waldeyerstraße 15, 48149
Münster, Germany E-mail:
[email protected] Keywords: C-C bond formation • DFT calculation • [3,3]-sigmatropic rearrangement • SF5chemistry • synthesis.
Abstract: Earlier studies have shown that [3,3]-sigmatropic rearrangements of allyl esters are useful for the construction of fluorine-containing carboxylic acid derivatives. This paper describes the synthesis of 3-aryl-pent-4-enoic acid derivatives bearing either a pentafluorosulfanyl (SF5) or a trifluoromethyl (CF3) substituent in the 2-position by treatment of corresponding SF5 or CF3 acetates of p-substituted cinnamyl alcohols with trimethylamine followed by trimethylsilyl triflate (TMSOTf). This Ireland-Claisen rearrangement delivered approximate 1:1 mixtures of syn/anti-diastereoisomers due to tiny differences (
