0 Hits

  • Previous / Next

You are using Science Of Synthesis as a Guest.
Please login or sign up for a free trial to access the full content. 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.

Meeeee 88 Meeeee-Meeeeeeee Meeeeeeeeeeeeeeeee ee Meeeeeee[‌88‌]

Meeeeeeeeee 88

Me8 Meeee (%) Mee
Me 88 [‌88‌]
8-MeMM8M8 88 [‌88‌]
8-MeM8M8 88 [‌88‌]
8-MeM8MM8M8 88 [‌88‌]
8-MeM8M8 88 [‌88‌]
8-MMM8M8 88 [‌88‌]

Meeeee 88 Meeeeeee Meeeeeeee eee Meeeee-Meeeeeeee Meeeeeeeeeeeeeeeee ee Meeeeeee[‌88‌]

Meeeee ee eee eeee eeee, Meeeeee eee Meeeee eeeeeeee e eee MMeM-eeeeee-eeee eeeeeeeee eeeeeee 88, eeeee eeeeeeeee eeeeeeeeeeeeeeeeee ee eeeeeee eeeee eeeeeeeeeeeeeeee ee e eeeeeeeeeeeeee eeeeeeeee. Meeeeeeee ee eeeeeee eee eeeeeeeeeeeeeeee eeee e eeeeeeeee eeeeee ee 88 eeeeeee β,γ-eeeeeeeeeee eeeeeeeeee eeeee 88 ee 88 eeeee 8 eeeeeeeeee ee eeeeee eeeeeee (Meeeee 88).[‌88‌]

Meeeee 88 Meeeeeeeeeeeeeeeee ee Meeeeee[‌88‌]

Meeeeeeeeee 88

M8 Meeee (%) Mee
(MM8)8MMMMMM 88 [‌88‌]
(MM8)8MMe eeeee [‌88‌]
(MM8)8MM=MMe8 88 [‌88‌]

Meeeeeeeeee 88M

M Meeee (%) Mee
MMee 88 [‌88‌]
88 [‌88‌]
M=M 88 [‌88‌]

Me eeeeee ee eeeee eeee eee eeeeeeee ee 8,8-eeeeeeeeeeeee eeeeeee eeeeeeee eeeeeeeeeeeeeeee ee eeee eeeeeeeeeeeee eeeeee α-eeeeeeeeee β,γ-eeeeeeeeeee eeeeeeeeee eeeee ee eeee eeeee. M eeeeeee ee eeeeeeeeee eeeeee eeee ee eeeeee, eeeee, eeeee, eeeeee, eeeee, eee eeeeeeeee eee eeeeeeeee eeeee eee eeeeeeee eeeeeeeeee, eeeeeeeeeeeee eeee eeeeeeeee eeeeeee. Mee eeeeeeee ee eeeeeeee ee eeeee eeee eee eeeeeeeeee ee eeeeeeeee eeeeeee eeeeeee 88 eeeeeee e MMeM-eeeeee eeeeee eeeeeee eeeeeeeeeeeeeee ee eeeeeeeeeeeeeeee ee 88 eeeeeeee ee β-eeeeeee eeeeeeeeeee (Meeeee 88). Meeeeeeeeeeeeee ee eee eeeeee eeeee σ-eeeeeeeeeeeeee eeeeeee 88, eeeee eeeeeeeee eeeeeeeeeeee eeeeeeee ee eeeeee eeeeeee eeeeeeeeeeeeeeee ee eeeee eeeeeeeee eeeeeeeeeee 88. Mee eeeeeeeeeeeee eeeeee eeeeeeeee eeeeeee eeeeeee 88 ee eeeeeeeeeee eeeeeee eeeeeeeeeeeeeee ee eee eeeeeeeee eeeeeeeeeee 88 eeee eeeeeeeeeeeeeeee.

Meeeee 88 Meeeeeee Meeeeeeee eee Meeeeeeeeeeeeeeeee ee Meeeeee[‌88‌]

Meeeeeeeeee, eee eeeeeeee ee eeeeeeeeee ee 8,8-eeeee eeeeeeeeee, eeee ee eeeee eee eeeeee eeeeeeeee, eeeeeeee eeeeeeee eeeeeeeeee ee eeeeeeeeee eeeeeeeee (Meeee 8).[‌88‌] Mee eeeeeeee ee eee eeeeeeee ee eeeee eeee eee eeeeeeee eeeeeee (MMMe) eeeee ee ee 888. Meeee eeeeeeeeeeeeee 8,8-eeeeee eee eeee eeeeeeeeee ee eee eeeeeeee ee ee eee eeee ee eeeeeee, eeeeeeeee e eeeeeeeee eeeeee eee eee eeeeeeeee ee β,γ-eeeeeeeeeee eeeeeeeeee eeeee. Meee ee eee eeeee eeeeeee ee eee eeeeeeeee 8:8 eeeeeeee ee 8,8-eeeeee eee eeeeee eeeeeee ee eeeeeee ee eeeeeeeee eeeeeeeee ee β,γ-eeeeeeeeeee eeeeeeeeee eeeee ee eeeeeeee ee eee eeeeeeeee(8)-eeeeeeeee 8:8 eeeeeeee eeeeee δ-eeeeeeee (eee Meeeee 8).

Meeee 8 Meeeeeeeeeeeeeeeee ee 8,8-Meeeee[‌88‌,‌88‌]

Meeeeeee Meeeeeee Meeeeee(e) MMMe Mee
888 [‌88‌]
888 [‌88‌]
888 [‌88‌]
888 [‌88‌]
888 [‌88‌]

e Meeeeeee eeeeee.

Meeeee(8)-eeeeeeeee eeeeeeeeeeeeeeeeee ee eeeeeee eee eeee eeeeeeeee eeeeeeeee eeeeeeeeeee ee e eeeeeeeeeeeeee eeeeeeeee (Meeeee 88).[‌88‌] Mee eeeeeeee eeeeeeee eeee eeeeeee eeeeeeee eeeeeee ee eee eeeeeeee ee e eeeeeeeee eeeeee ee eee(η8-eeeeeeeee-8,8-eeeee)eeeeee(8) [Me(eee)8], 8 eeeeeeeeeee ee eeeeeeeeeee, eee 8 eeeeeeeeee ee eeeeee eeeeeeee ee e eee eeeeeeee eeeee 8 eeeeeeeeee ee eeeeee eeeeeee, eeeeee α,β-eeeeeeeeeee eeeeeeeeee eeeee 88 ee eeee eeeee. Mee 8-eeeeeeeeeeeeeeeeee eeeeee eeeee eeee ee e eeeeeeeee eeeee ee eeee eeeeeeeee eeeeeeeeeeeeeeee. Meeeeeeeeee eeeeeeeeeeeeee eeeeeee eeee eee eeeeeeee eee eee eeeeeee eeeeeee eeeeeeeee eeeeeeee ee eeeeee eeeeeee eee eeeeeee, eee eeeeee eeeeeee eeeeeeeeeeeeee ee eeeeeee ee eeee eeeeeeeeeee eeeeeee 88 (Meeeee 88). Meeeee–eeeeee eeeeeee eeeeeee 88, eeeee ee eeeeee ee eee eeeeeeee ee eeeeee(8) eeee eeeeee eeeeeee, eeeeeeeee eeeeeeeeeeeeeee eeee eee eeeeeeeeeeee 88, eee eeeeeeeeee eeeeeeeee eeeeeeeeeee eeee eeeeeeeeeeee 88 eeeee eee eeeeeee.

Meeeee 88 Meeeeeeeeeeeeeeeee ee Meeeeee[‌88‌]

Meeeeeeeeee 88

M8 M8 Meeee (%) Mee
Me Me 88 [‌88‌]
Me Me 88 [‌88‌]
e-Me Me 88 [‌88‌]
Me 8-MeMMM8M8 88e [‌88‌]

e Me MMMM.

Meeeee 88 Meeeeeee Meeeeeeee eee Meeeeeeeeeeeeeeeee ee Meeeeee[‌88‌]

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 α-(8-eeeeeeeeeeee) α,β-eeeeeeeeeee eeeeeeeeee eeeee 88, eeeee eee eeeeee eeeeeeeeeee eeee α-eeeeeeeeee γ-eeeeeeeeeeeeee 88 eeeee eeeeee eeeeeeeeee.

Meeeee 88 Meeeeeeeeeeeeeeeeee ee Meeeeee[‌88‌]

Meeeeeeeeee 88

M8 M8 M8 M8 Meeee (%) Mee
(MM8)8Me M M M 88 [‌88‌]
Me Me M M 88 [‌88‌]
Me M Me M 88 [‌88‌]
8-MeMM8M8 M Me Me 88 [‌88‌]

Meeeeeeeeeee Meeeeeeee

β,γ-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.

MMeM-eeeeee eeeeeeeee eeeeeeee 88 (8.8 ee, 8.8 µeee) eee eeeeee ee e 88-eM eee-eeeeee eeeee eee e eeee ee eee eeeeee (8.88 eeee) ee MMM (88.8 eM) eee eeeee eeeee eeeee. Mee eeeee eeeeeeeeee eee eeeeeeee ee MM8 eeeee e eeeeeee, eeee e 8.88 M eeee ee Me8Me ee eeeeeee (8.88 eM, 8.88 eeee) eee eeeee ee ee, eee eee eeeeeee eee eeeeeee ee eee eeee eeeeeeeeeee ee 88 °M eee 88–88 e. 8 M ee MMe eee eeeee, eee eeeeeee eee eeeeeeeee eeee Me8M (8 ×), eee eee eeeeeeee eeeeeee eeeeee eeee eeeeeeeee eeee ee MeMM (8 ×). Mee eeeeeeee eeeeeee eeeeee eeee eeeeeeeee eeee ee MMe, eeee eeeeeeeee eeee Me8M (8 ×), eeeeee eeee eee. ee MeMe, eee eeeee (MeMM8). Meeee eeeeeee ee eee eeeeeee eeeee eeeeeee eeeeeeee, eee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee) ee eeeeee 88 ee 88 ee e eeeeee eeeeeeeeeee.