Asymmetric bond transformations play a key role in contemporary organic chemistry. In order to mediate these processes, extensive research has been devoted to identifying chiral reagents capable of yielding high selectivities for broad classes of transformations. One such class of compound, binol, a �privileged chiral ligand�, has been used extensively for organo, early-to-mid transition-metal, and lanthanide-catalyzed processes. Conspicuously absent are studies applying this ligand to late-transition-metal catalyzed processes, which is likely due, in part, to the mis-match between hard-aryloxide and soft-metal coordination characteristics. In order to make late transition metal binding more robust, we present a new class of L2X2 binolate ligand that displays silyl-linked Lewis-basic residues at the 3,3'-positions. A modular synthetic approach has been identified to access these ligands by applying Gevorgyan's Rh2(OAc)4-catalyzed silane/aryl iodide coupling. Insights into the coordination characteristics of first and second-row late-transition metal complexes will be presented as well as preliminary insights into their ability to catalyze organic transformations.

New class of multifunctional binolate ligand: Synthesis, characterization, and applications toward catalysis

247th National Meeting (2014)

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