Rhodium-Catalyzed Formal C-O Insertion in Carbene/Alkyne Metathesis Reactions: Synthesis of 3-Substituted 3 H-Indol-3-ols.

An efficient and novel rhodium-catalyzed formal C-O insertion reaction of alkyne-tethered diazo compounds for the synthesis of 3 H-indol-3-ols is described. A type of donor/donor rhodium carbene generated in situ via a carbene/alkyne metathesis (CAM) process is the key intermediate and terminates in a unique transformation different from donor/acceptor carbenoids. In addition, 18O-labeling experiments indicate that intramolecular oxygen-atom transfer from the amide group to the carbon-carbon triple bond occurs during this transformation.