01/2017

Many site-selective palladium-catalyzed C–H functionalization methods require directing groups. We report here β-carboline amides as intrinsic directing groups for C(sp²)–H functionalization.

Various substrates including the natural product alangiobussinine and the marinacarboline core structure were functionalized using carboline-directed δ-C(sp²)–H alkynylations. This transformation proceeds under mild conditions and is compatible with a wide variety of β-arylethamines.

δ-Alkynylation of β-arylethamines via a six-membered palladacycle is favored over γ-C(sp²)–H bond functionalization when both positions are accessible. The versatility of β-carboline amides as directing groups is evidenced by other δ-C(sp²)–H functionalizations such as alkenylation, arylation, and C–N bond formation.