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1.1.8.3.1 Nickel- or Palladium-Catalyzed Hydrocarboxylation of Alkenes, Dienes, and Alkynes

DOI: 10.1055/sos-SD-212-00170

Takaya, J.; Iwasawa, N.Science of Synthesis: C-1 Building Blocks in Organic Synthesis, (20141295.

In 2008, a nickel-catalyzed hydrocarboxylation of styrene derivatives was reported using diethylzinc as a stoichiometric reductant.[‌41‌] The reaction of various styrene derivatives 42 and diethylzinc proceeds smoothly in the presence of a catalytic amount of bis(acetylacetonato)nickel(II) [Ni(acac)2] and cesium carbonate under atmospheric pressure of carbon dioxide, affording α-arylpropanoic acids 43 in good yield (Scheme 13). Electron-deficient styrene derivatives show good reactivity. The reaction is proposed to proceed via generation of nickel hydride complex 44, which undergoes hydrometalation of styrene to give 1-phenylethylnickel complex 45 (Scheme 14). The formed complex 45 is converted into 1-phenylethylzinc 46 and ethylnickel complex 47 by transmetalation with diethylzinc. Ethylnickel 47 undergoes β-hydride elimination to regenerate nickel hydride complex 44. There exists a separate catalytic cycle involving transmetalation of 46 back to nickel to form 1-phenylethylnickel complex 45, which reacts with carbon dioxide to give nickel carboxylate 48. Nickel carboxylate 48 is also converted into ethylnickel complex 47 by transmetalation with diethylzinc. This is a quite rare example of a homogeneous catalytic carbon dioxide fixation reaction with alkenes.

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References


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