We report a hydroaminative cyclization of enynes using phosphine-quinolinolato rhodium catalysts. The hydroaminative cyclization of 2-vinylphenylacetylene derivatives with secondary amines gives 2-aminoindenes in good yields. The reaction is considered to proceed through carbon-carbon bond formation on a catalytically generated aminocarbene ligand.

Anti-Markovnikov hydroamination of both aliphatic and aromatic terminal alkynes with primary amines was achieved using an 8-quinolinolato rhodium catalyst to form aldimines and enamines in high yields. This catalytic system realized high functional group tolerance including hydroxy, bromo, cyano, and thioester groups.

Both 2:1 and 1:1 couplings of alkylacetylenes with secondary amines were achieved using 8-quinolinolato rhodium catalysts and CsF. The 2:1/1:1 selectivity was switched by choosing the reaction solvent. In DMA, an unprecedented 2:1 coupling reaction of alkylacetylenes with amines proceeded to give 2-aminodiene products. One-pot 2:1 coupling/reduction provided rapid access to various allylamines, while one-pot coupling/hydrolysis gave enones as products. In toluene, anti-Markovnikov hydroamination occurred under relatively mild conditions to give 1:1 coupling products.

Anti‐Markovnikov addition of anilines to aliphatic terminal alkynes proceeded using an 8‐quinolinolato rhodium/phosphine catalyst system. The use of a strong organic base, 1,1,3,3,–tetramethylguanidine, in the catalyst system enabled the formation of the aldimine products. Substrates with various functional groups including polar groups such as a phenolic hydroxy group are applicable to the hydroamination.

We report a hydroaminative cyclization of enynes using phosphine‐quinolinolato rhodium catalysts. The hydroaminative cyclization of 2‐vinylphenylacetylene derivatives with secondary amines gives 2‐aminoindenes in good yields. The reaction is considered to proceed through carbon–carbon bond formation on a catalytically generated aminocarbene ligand.