The Kumada cross-coupling reaction uses a palladium or nickel catalyst to couple an organohalide and a Grignard or organolithium reagent. The mechanism follows the expected oxidative addition-reductive elimination cycle.

• Organolithium reagents are highly versatile as they can be prepared in multiple ways, including the direct lithiation of hydrocarbons.
• Fast addition of the organolithium produces α-bromo alkenyllithiums that undergo rearrangement to give lithium acetylides, lowering yields.
• No reagents should be added in excess and the Pd⁽⁰⁾ catalyst should be clean to facilitate good yields.
• Base-sensitive functional groups are not tolerated as they will react with the Grignard or organolithium reagent. Tolerance is improved with the Negishi cross-coupling, which uses organozinc reagents instead.

• Reagents: Catalytic Palladium or Nickel
• Reactant: Organohalide, Organomagnesium or Organolithium
• Product: Coupled Product
• Type of Reaction: C-C Cross-Coupling

Mechanism

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