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Palladium-catalyzed carbonylation reactions have already become a true toolbox in modern organic synthesis. By using CO as an inexpensive C1 source, valuable carbonyl-containing compounds are selectively produced. Among the nucleophiles applied, in addition to oxygen and nitrogen species, various carbon nucleophiles such as alkenes, alkynes, organometallic reagents and even C–H acidic compounds can be applied under certain conditions. In this chapter, the achievements on this topic are summarized and discussed. Alkenones, alkynones and ketones can be produced effectively via carbonylative Heck reactions, carbonylative Sonogashira reactions and carbonylative Suzuki reactions. As an attractive topic of current interest, carbonylative C–H activation reactions have been included in the discussion.

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