Pd(II)-catalysed C-H functionalisation of indoles and pyrroles assisted by the removable N-(2-pyridyl)sulfonyl group: C2-alkenylation and dehydrogenative homocoupling.

The easily installed and removed N-(2-pyridyl)sulfonyl group exerts complete C2 regiocontrol over the Pd(II)-catalysed C-H alkenylation of indoles and pyrroles, affording the corresponding products in good isolated yields (typically > or = 70 %). A remarkable feature of this catalyst system is that it tolerates a wide variety of substituted alkenes, including conjugated electron-deficient alkenes, styrenes and 1,3-dienes, as well as conjugated 1,1- and 1,2-disubstituted olefins. The final reductive desulfonylation affords the C2-substituted, free-NH indoles and pyrroles in good yield. This N-(2-pyridyl)sulfonyl-directing strategy has also been extended to the development of a protocol for the intermolecular, dehydrogenative homocoupling of indoles, providing 2,2'-biindoles. Mechanistic work based upon reactions with isotopically labelled starting materials and competitive kinetic studies of electronically varied substrates suggests a chelation-assisted electrophilic aromatic substitution palladation mechanism.