Ligand-controlled, norbornene-mediated, regio- and diastereoselective rhodium-catalyzed intramolecular alkene hydrosilylation of homoallyl silyl ethers (1) exploiting either BINAP or 1,6-bis(diphenylphosphino)hexane (dpph) has been developed. This method permits selective access to either trans-oxasilacyclopentanes (trans-2) or oxasilacyclohexanes (3) at will. A substoichiometric amount of norbornene markedly increased both yield and selectivity. A norbornene-mediated hydride shuttle process is discussed.
Cooperation between a Lewis base and Pd catalyst enables the direct enantioselective α-functionalization of aryl and vinyl acetic acid esters using a bifunctional B(pin)-substituted electrophile. Critical to the success of this method was the recognition that both catalysts could control the necessary stereochemical aspects; the Lewis base catalyst controls the enantioselectivity of the reaction, whereas the Pd catalyst regulates alkenyl-B(pin) configuration. This is the first example of using cooperative catalysis to control both stereochemical features during Pd-catalyzed allylic alkylation.
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