Activation of unsaturated substrates by Au(I)-catalysts is a well established methodology for achieving molecular complexity under mild conditions. While the enantioselectivity of such reactions has been the focus of much recent work, regioselectivity has received less attention. We show that the regioselectivity of the Au(I)-catalyzed rearrangement of meta-substituted aryl alkynyl sulfoxides can be controlled by modulating the electrostatic interaction between the cationic catalyst and its counterion. The extent of ion pairing in solution determines the regioselectivity of the catalyst, significantly enhancing the selectivity imparted by the ligand structure. This represents a convenient strategy for achieving or enhancing reaction selectivity independent of ligand design.

Counterion and solvent induced control of regioselectivity in the Au(I)-catalyzed rearrangement of alkynyl sulfoxides

248th National Meeting (2014)

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