The catalytic asymmetric aza-ene reactions of 3-indolylmethanols with cyclic enaminones and the highly enantioselective aza-ene reactions utilizing cyclic aza-ene components have been established, which directly assemble isatin-derived 3-indolylmethanols and dimedone-derived enaminones into C3-functionalized chiral indoles with one all-carbon quaternary stereogenic center in high yields and excellent enantioselectivities (up to 99% yield, up to 95:5 er).

The catalytic enantioselective arylation of 3‐indolylmethanols has been established in an atom‐economic fashion, which assembles isatin‐derived 3‐indolylmethanols and 3‐methylindoles into biologically important 3,3′‐bis(indolyl)oxindoles bearing a quaternary stereogenic center in high yields and good enantioselectivities (≈99 % yield and 91:9 enantiomeric ratio). This reaction also represents the catalytic enantioselective synthesis of 3,3′‐bis(indolyl)oxindoles, which is applicable to a wide range of substrates, yielding a series of chiral 3,3′‐bis‐ (indolyl)oxindoles with structural diversity. Control experiments demonstrated that the NH group in the indole moiety of 3‐indolylmethanol is important in obtaining good enantioselectivity, whereas the NH group of 3‐methylindole plays a crucial role in the reactivity via the hydrogen bonding interaction with the catalyst.

The title reaction has been established to construct indole-fused five-membered rings in good yields (up to 86%).

13 7,12,i]xanthene-5,7,12,14(13H)-tetraones have been synthesized in high yields in the presence of [bmim ＋ ][ 4 BF -] as an ionic liquid. The reaction work-up is simple and the ionic liquid can be easily separated from the product and reused.

An organocatalytic asymmetric approach has been developed for the ennantioselective construction of dihydroisocoumarin‐based spirooxindole frameworks in high yields, excellent diastereo‐ and enantioselectivities (up to 99%, all >95:5 dr, up to 99% ee). This approach takes advantage of chiral thiourea‐tertiaryamine catalyzed tandem reaction of isatins with enolizable homophthalic anhydride, which has wide substrate scope and can be performed with low catalyst loading. This reaction not only provides an efficient and useful method for constructing enantioenriched dihydroisocoumarin‐based spirooxindole scaffold, but also will enrich the research contents of catalytic asymmetric tandem reactions and enantioselective synthesis of biologically important spirooxindoles.magnified image