Typical ancillary ligands are anionic or neutral species. Cationic ones are exceptions and, when used, the positively charged groups are normally attached to the periphery of the donating atom. However, a series of recent experimental, as well as theoretical results, suggest that the utility in catalysis of cationic phosphines with no spacer between the phosphorus atom and the positively charged group(s) has been largely overlooked. In fact, these cationic ligands depict excellent p-acceptor character that can exceed that of phosphites or polyfluorinated phosphines and this property can be used to extraordinarily enhance the Lewis acidity of the metals they coordinate. Specifically, new high reactive p-acid catalysts, mainly based on Pt(II) and Au(I), will be presented and their superior performance demonstrated along several mechanistically distinct transformations and on the synthesis of natural products.

Cationic phosphines: Synthesis and applications

248th National Meeting (2014)

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