Experimental Results and Mechanistic Insights on the Reactions of Indolylmethyl Acetates with Soft Carbon Pronucleophiles

The palladium-catalyzed reaction of N-protected 2-indolylmethyl acetates with soft carbon pronucleophiles is described. Besides the formation of the expected coupling reaction at the C1 ' position, unprecedented attack at the C3 position of the plausible eta(3)-indolyl-palladium intermediate has been observed, and the selectivity control C1 '/C3 seems to depend on the nature of the protecting group and ligand. The reactivity of 3-indolylmethyl acetates has also been also investigated. Quantum chemical calculations support the experimental results.