Ir-catalyzed sp(3) C-H alkylation of γ-butyrolactam with alkenes was used for the highly enantioselective synthesis of 5-substituted γ-lactams, which were readily converted into chiral 4-substituted γ-amino acids. A broad scope of alkenes was amenable as coupling partners, and the alkylated product using acrylate could be transformed into the key intermediate of pyrrolam A synthesis.

4-Substituted tryptophan derivatives and the total synthesis of cis-clavicipitic acid were achieved in reactions in which Ir-catalyzed C-H bond activation was a key step. The starting material for these reactions is asparagine, which is a cheap natural amino acid. The reductive amination step from the 4-substituted tryptophan derivative gave cis-clavicipitic acid with perfect diastereoselectivity.

A new π‐conjugated system of nitrogen‐containing polycyclic compounds was constructed by cationic AuI‐catalyzed cycloisomerization. Intramolecular reaction of 9‐(2‐alkynylphenyl)‐9H‐carbazole derivatives gave a variety of penta‐ and hexacyclic compounds possessing a dibenzazepine skeleton. The rigid carbazole structure was responsible for efficient 7‐endo‐dig cycloisomerization.

Enantioselective synthesis of azepine-fused planar-chiral ferrocenes was achieved by the chiral cationic Pt-catalyzed intramolecular cycloisomerization of N-propargyl-2-ferrocenylanilines. A mechanistic study using an N-allenyl analogue indicated that the reaction proceeded selectively in a 7-exo-dig manner along with isomerization of the exo-olefin moiety. A methanesulfonylamino tether was crucial for selective cycloisomerization. This is the first example of the enantioselective synthesis of heteropin-fused planar-chiral ferrocenes.