This review summarizes the recent advances in the field of asymmetric dearomatization of phenols and their applications in the total synthesis of some complex natural products.

The first chiral phosphoric acid catalyzed highly diastereo- and enantioselective 1,3-dipolar cycloaddition reaction of azlactones and methyleneindolinones was disclosed. By using a BINOL-derived chiral phosphoric acid as the catalyst, azlactones were activated as chiral anti N-protonated 1,3-dipoles to react with methyleneindolinones to yield biologically important 3,3′-pyrrolidonyl spirooxindole scaffolds in high yields, with good-to-excellent diastereo- and enantioselectivity.

The copper-catalyzed cascade azidation–cyclization of tryptophols and tryptamines has been developed.