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A new palladium-catalyzed domino approach for the synthesis of attractive spirocyclic indolines and dihydrobenzofurans was developed. The reaction proceeds through a sequential intramolecular Heck spirocyclization, remote C-H activation, and diazocarbonyl carbene insertion. Various spiroindolines and spirodihydrobenzofurans containing two quartenary carbon stereocenters were readily obtained in good to excellent yields. A preliminary study of asymmetric spirocyclization using chiral monophosphoramidite as a ligand was also conducted, enabling access to highly valuable chiral spiroindolines with up to 80% ee.

An asymmetric dual-metal relay catalysis strategy that combines Rh/chiral sulfur-olefin-catalyzed enantioselective 1,2-addition with a Pd-catalyzed intramolecular C-O coupling has been developed. The method allows rapid and efficient synthesis of quaternary carbon-containing gem-diaryl benzofuran-3(2H)-ones in good yields in a highly enantioselective manner (up to 99% ee) through a simple one-pot cascade reaction.

A rhodium-catalyzed stepwise asymmetric 1,4- and 1,2-addition of arylboronic acids to α,β-unsaturated cyclic N-sulfonyl ketimines has been developed, providing a wide range of gem-diaryl-substituted chiral benzosulfamidates with high optical purities. C1-Symmetric chiral diene and branched chiral sulfur-olefin ligands were sequentially utilized in this double-arylation process for high stereocontrol. Further synthetic utility offers new opportunities for the facile construction of otherwise difficult to access polycyclic heterocycles.

With the use of a simple sulfur–olefin ligand, a highly enantioselective rhodium-catalyzed addition of arylboroxines to N,N-dimethylsulfamoyl-protected aldimines has been achieved, allowing access to a broad range of chiral diarylmethylamines in high yields (up to 98%) with uniformly excellent enantioselectivities (up to 99% ee). This catalyst system is also applicable to the arylation of N-tosyl arylimines. By utilizing this method, some biologically active molecules possessing a chiral 1-aryl-1,2,3,4-tetrahydroisoquinoline core such as Solifenacin and (S)-(+)-Cryptostyline II are facilely constructed.

The first example of nickel-catalyzed asymmetric Ullmann coupling of bis-ortho-substituted arylhalides is described. With the chiral BINOL-based monodentate phosphoramidite ligand, the reaction allows atropoenantioselective synthesis of a series of axially chiral tetra-ortho-substituted biaryl dials. By taking advantage on this asymmetric Ullman coupling as a key stereogenic axis-forming reaction, the formal synthesis of (+)-isoschizandrin was accomplished.

A novel iron-catalyzed intermolecular decarboxylative Csp(3)-Csp(2) coupling reaction using proline derivatives as starting materials is developed. In this process, a series of potentially useful ligands (tertiary aminonaphthol) for catalysis was obtained.