BINOLs, BINAPs, and their derivatives can facilitate a huge set of enantioselective reactions, involving carbon-carbon or carbon-heteroatom bond formation. Preparation of such important chiral scaffolds, however, requires a multi-step sequence including protecting group manipulation, multiple purifications of many intermediates, the use of a large amount of organolithium reagents. Efficient syntheses of the 3,3’-bis-substituted BINOLs and other biphenol compounds were achieved through reductive arene C–H silylation of bis-acetyl BINOL and biphenols. This approach involved a one-pot, Ir-catalyzed ester hydrosilylation with dialkyldihydrosilanes followed by Rh-catalyzed cross-dehydrogenative <i>ortho</i>-C–H silylation. A library of 3,3’-bis-silyl-BINOLs and biphenols (20 examples) was produced by addition of a series of organometallic nucleophiles and oxyanion nucleophiles to the resulting bis-dioxasilines. This streamlined catalytic method will potentially expand the scope of chiral supporting ligands.

Catalytic 3,3’-bis-functionalization of BINOLs and biphenols

2019 Spring National Meeting

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