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Takaya, J.; Iwasawa, N., Science of Synthesis: C-1 Building Blocks in Organic Synthesis, (2014) 1, 295.
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 a-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 B-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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Meeeee 88 Meeeeeeeeeeeeeeeee ee Meeeeee[88]
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Meeeee 88 Meeeeeeeeeeeeeeeee ee Meeeeee[88]
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Meeee ee eee eeee eeeeeeee, e eeeeee-eeeeeeeee eeeeeeeeeeeeeeeeeee ee eeeeeeeeeeeeeee eeeeeeee eee eeee eeeeeeeee eeeee eeeeeeeeeeee ee e eeeeeeeeeee eeeeeee (Meeeee 88).[88] Mee eeeeeeeeeeeee eeeeeeee ee e eeeeee eeeeeeeeeeeeeee eeeeee eee ee eee eeeeeee eeeeee ee eeee a-(8-eeeeeeeeeeee) a,B-eeeeeeeeeee eeeeeeeeee eeeee 88, eeeee eee eeeeee eeeeeeeeeee eeee a-eeeeeeeeee Y-eeeeeeeeeeeeee 88 eeeee eeeeee eeeeeeeeee.
Meeeee 88 Meeeeeeeeeeeeeeeeee ee Meeeeee[88]
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B,Y-Meeeeeeeeee Meeeeeeeee Meeee 88 ee 88; Meeeeee Meeeeeeee:[88]
MMMMMMM: Meeee-eeeee eeeeeeeeeeeeeeeee eee eeeeeeeeee. Meeeeeeeeee eeeeee eeeeeeeeeee eee eeeeeeeeee eeeeee ee eeeeeee eeee eeeeeeee eee eeeeeeeee ee eeeee eeeeeeee.
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References
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