Nucleophile-Controlled Trapping of Gold Carbene by Nitriles and Water: Synthesis of 5H‑Pyrimido[5,4‑b]indoles and 2‑Benzylidene-3-indolinones

A gold-catalyzed, nucleophile-controlled cascade reaction of N-(2-azidophenyl-ynyl)methanesulfonamides with nitriles and water is described that provides structurally diverse 5H-pyrimido[5,4-b]indoles and 2-benzylidene-3-indolinones in good to excellent yields. Mechanistic studies indicate that the β-sulfonamido-α-imino gold carbene is the key intermediate which is generated through the gold-catalyzed cyclization of N-(2-azidophenyl-ynyl)methanesulfonamides and undergoes formal [4 + 2] cascade annulation with nitriles and intramolecular S_N2′ type reaction with water, respectively.