Carbon–Carbon Bond Formation via Catalytically Generated Aminocarbene Complexes: Rhodium‐Catalyzed Hydroaminative Cyclization of Enynes with Secondary Amines

Abstract

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 Addition of Anilines to Aliphatic Terminal Alkynes Catalyzed by an 8‐Quinolinolato Rhodium Complex

“…Examination on the substrate scope including functional group compatibility was limited in both cases, and further investigations were desired for the catalytic anti‐ Markovnikov addition of anilines to aliphatic terminal alkynes. Our group has been studying catalytic transformation of terminal alkynes using 8‐quinolinolato rhodium/phosphine catalyst systems [20–29] and developed anti‐ Markovnikov addition of both aliphatic primary [29] and secondary amines [22,28] to terminal alkynes ( Scheme 1 ,c ). One of the features of the 8‐quinolinolato‐rhodium‐catalyzed hydroamination is the remarkably high functional group tolerance, which prompted us to investigate the hydroamination of aliphatic terminal alkynes with anilines.…”