Pd-Catalyzed Vicinal Intermolecular Annulations of Iodoarenes, Indoles, and Carbazoles with Enynes.

Reaching the formidable C-H corners has been one of the top priorities of organic chemists in the recent past. This prompted us to disclose herein a vicinal annulation of 2-iodo benzoates, indoles, and carbazoles with N-embedded 1,6-enynes through 7-/8-membered palladacycles. The relay does not require the assistance of any directing group, leading to multicyclic scaffolds, which are readily diversified to an array of adducts (with new functional tethers and/or three contiguous stereocenters), in which we showcase a rare benzylic mono-oxygenation.

Rh-catalyzed chemo-, stereo- and regioselective C-H cascade annulation of indolyloxopropanenitriles for pyranoindoles.

Selective annulations of alkynes represent a powerful tool for constructing multicyclic scaffolds while installing desired substitution patterns with precision. Herein, we report a Rh-catalyzed unique annulation of indolyl oxopropanenitrile with hydroxy-alkynoates to access pyranoindole cyclic motifs, featuring enol oxygen as a rare chemoselective reactive terminal. The reaction proceeds via a five-membered oxy-rodacycle through C-H activation by a rhodium complex guided by enolic- and propargyloxy dual co-ordination to enable a regio- and stereoselective modular assembly.