Enantioselective Syntheses of Tricyclic Benzimidazoles via Intramolecular Allylic Aminations with Chiral-Bridged Biphenyl Phosphoramidite Ligands.

The first iridium-catalyzed enantioselective intramolecular allylic aminations of benzimidazole-tethered allylic carbonates were developed, providing three classes of tricyclic benzimidazoles bearing a tertiary carbon stereogenic center in high yields and excellent enantioselectivities (up to 99% yield, 99% ee). Wide substrate scope, excellent catalytic efficiency and mild conditions rendered this protocol particularly superior and practical. Impressively, the chiral bridge with a tunable structure was shown to provide a very good adjustment space for the chiral environment. The excellent catalytic performance of the ligands manifested their advantages over the bisphenol-based and BINOL-derived counterparts in these transformations. It also highlighted the potential application value of the chiral-bridged ligands.