The pentafluorosulfanyl (SF5) group has become one of the most interesting fluorine-containing substituents due to its outstanding properties.1 The most used synthetic strategy towards aliphatic SF5-compounds is based on the addition of SF5X (X = Cl, Br) across multiple bonds.2 The addition of SF5Cl to ketene delivers SF5-acetyl chloride3 which can be esterified with a series of 3-hydroxyalk-1-enes. Recently, we have shown that these allylic esters are useful substrates for Ireland-Claisen rearrangement to give different a-SF5-substituted carboxylic acids. So far, only esters of secondary allylic alcohols could be used as starting materials for the rearrangement giving moderate yields of the target products.Now modifications of the reaction conditions led to improved yields and additionally enables the use of esters of primary allylic alcohols such as cinnamylic alcohols to give the target carboxylic acids as almost 1:1 mixtures of diastereoisomers. All reactions were also performed with the corresponding trifluoropropionates in order to compare SF5- and CF3-containing substrates. Figure 1. <img src='https://acs-archive-assets2.s3.amazonaws.com/241nm/uploads/67111__figure1_.jpg' alt='' /> 1. S. Altomonte, M. Zanda, J. Fluorine Chem. 2012 , 143, 57.2. W. R. Dolbier, Jr., S. A�t-Mohand, T. D. Schertz, T. A. Sergeeva, J. A. Cradlebaugh, A. Mitani, G. L. Gard, R. W. Winter, J. S. Thrasher, J. Fluorine Chem. 2006 , 127, 1302.3. G. Kleemann, K. Seppelt, Angew. Chem. 1978 , 90, 547.

Pentalfuorosulfanylacetyl chloride: A versatile building block

248th National Meeting (2014)

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