Using the approach of catalyst scaffold optimization, a series of closely related self-assembled ligands (SALs) were prepared. When combined with Rh(I) catalyst precursors, the SALs produce a series of heterobimetallic supramolecular catalysts that prove to be very effective for the catalytic asymmetric hydroboration (CAHB) of 2- and 3-substituted styrene derivatives (i.e., X= -OMe, -Cl, -F, -CF3, and �Me); the regio- and enantioselectivities obtained rival or exceed the highest reported in the literature. While the nominal structures of these catalysts are quite similar, subtle structure differences are reflected in unique reactivity and selectivity. In analyzing the data, it was observed that some catalysts reacted much more readily with 2-substituted derivatives than with the 3-substituted isomers and vice versa. This was extended to a series of simple diene substrates with some further catalyst optimization. The process through which catalysts were developed and the results obtained for the catalyst-directed CAHB of either alkene in simple diene substrates will be discussed.

Site-selective supramolecular catalysts for catalytic asymmetric hydroboration

248th National Meeting (2014)

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