In 2000, Steglich et al. reported an intramolecular Pd(II)-mediated decarboxylative cross-coupling reaction in their synthesis of lamellarin L.
Myers et al. reported decarboxylative olefination of ortho-substituted arene carboxylates in the presence of an oxidant (Ag2CO3) in 2002.
Subsequent studies showed that homogeneous Pd catalysts were able to decarboxylate acids at lower temperatures than their Cu and Ag counterparts, but were limited to electron rich ortho-substituted aromatic carboxylic acids.
Despite this, palladium catalysts are able to promote a wide variety of cross-coupling reactions including biaryl formation and aryl alkyne formation, along with a variety of cross-coupling reactions in which the carboxylic acid is not bonded to an aromatic.
Other Pd-catalyzed decarboxylation cross-coupling reactions include conjugated diene preparation (see dienes and trienes below) and dehydrogenative reactions (with a variety of substrate and catalyst combinations).
Contrarily to Cu-only systems, decarboxylative palladation is the rate-limiting step in the palladium catalytic cycle.