The synthesis of a new class of chiral silanol-containing ligands is presented with applications for enantioselective catalysis. Designing silicon-containing ligands for asymmetric catalysis offers advantages because of the electropositive nature and size of silicon compared to carbon.  The ligand design incorporates both a silanol and a second chelating atom, and is proposed to bind to metals in a bidentate fashion.  NMR spectroscopy and mass spectrometry studies of metal-ligand binding interactions is used to understand the binding mode and ratio with a wide variety of Lewis acidic metals including AgOAc, Sc(OTf)3 and Ti(Oi-Pr)4.  The catalytic activity and asymmetric induction of the silanol�containing ligand has been evaluated with several carbon-carbon bond-forming cyclization reactions to access heterocycles and carbocycles. A modular ligand synthesis allows for the incorporation of substituents with various steric and electronic effects to understand the origins of enantioselectivity. Binding studies, catalytic activity and selectivity have been investigated and compared to known phosphine- and nitrogen-based ligands.

Design and synthesis of a chelating silanol ligand with applications for asymmetric catalysis

248th National Meeting (2014)

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