A new strategy for the highly efficient construction of functionalized phenanthridinones has been developed by starting from readily available acyclic α,β-unsaturated carbonyl compounds that have a 2-aminophenyl group at the β-position or carbonyl carbon and dimethyl glutaconate. The domino reaction involves an intermolecular [3+3] annulation followed by an intramolecular aza-cyclization/aromatization process and allows for the synthesis of polysubstituted dihydrophenanthridinone and phenanthridinone derivatives in high to excellent yields under extremely mild conditions (i.e., transition-metal-free and open to air) in a single step.

A new approach for the α-arylation of acetic acid through Pd-catalyzed silver-mediated direct CH arylation of acetic acid with aryl iodides was developed. This protocol provided a straightforward method for the synthesis of a diverse set of α-phenylacetic acids.

On the terminal diazo nitrogen atom, two CN bonds are formed in the bicyclization reaction of the readily available acyclic substrates with diazomethanes as 1,3-dipoles. The tandem 1,3-dipolar cycloaddition/intramolecular aza-addition/oxidative aromatization reaction can tolerate a variety of functional groups and proceeds under mild metal-free conditions to give substituted analogues of withasomnine alkaloids in good to high yields in a single step.

A new [3+2] cycloaddition strategy for the direct synthesis of highly substituted pyrroles from the readily available α-acylketene dithioacetals (or related substrates) and commercially available propargylamines under mild metal-free conditions has been developed. In this reaction, the acyl group plays a critical role in driving the conjugate addition of propargylamine and further cyclization to give pyrroles. Furthermore, the wide scope was confirmed by the preparation of 1,2,3,4-tetrasubstituted pyrroles (60–70% yields) via a formal 1,2-acyl migrating [3+2] cycloaddition pathway with N-methylprop-2-yn-1-amine as the secondary amine component.

The first proton-promoted intermolecular hydroamination reaction of the enynes, α,α-dialkynylketene S,S-acetals 2, is described. A series of benzo[b][1,4]diazepines, with the structures of 3 and 5, were prepared chemo- and regioselectively in good to high yields by reacting the readily available 1,4-diynes 2 with both terminal and internal alkyne functions with o-phenylenediamines under very mild conditions.