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18.2.16.1.1.3.1 Carboxylation of Organometallic Derivatives

DOI: 10.1055/sos-SD-118-00330

Braverman, S.; Cherkinsky, M.Science of Synthesis Knowledge Updates, (20143246.

Organolithium or Grignard reagents are the typical nucleophilic coupling partners in carboxylation reactions due to their high reactivity, which can easily overcome the high kinetic and thermodynamic stability of carbon dioxide. These carboxylation reactions proceed smoothly, even in the absence of transition-metal catalysts, and the use of organolithium or organomagnesium halides still represents an excellent method for the low-cost synthesis of carboxylic acids. However, these reactions are not compatible with sensitive functional groups, such as aldehydes, ketones, or nitriles, as such groups react rapidly with organolithium or Grignard reagents.

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Meeeeeeeeee 88

M8 Meeeee (%) Mee
8-MM8M8 88 [‌888‌]
8-MeM8M8 88 [‌888‌]
8-MeM8MM8M8 88 [‌888‌]
8-MeM8MM8M8 88 [‌888‌]
8-MMM8M8 88 [‌888‌]

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Meeee Me8 Meeeeeee Meeeee Meeeeeeeee Meeee (%) Mee
8 8-e-MeM8M8 [Me(MM)(eee)]8, MeM eeee eeeeeee, 88 °M 88 [‌888‌]
8 8-Me8M=MMM8M8 [Me(MM)(eee)]8, MeM eeee eeeeeee, 88 °M 88 [‌888‌]
8 8-MeMM8M8 [Me(MM)(eee)]8, MeM eeee eeeeeee, 88 °M 88 [‌888‌]
8 8-MM8M8 [Me(MM)(eee)]8, MeM eeee eeeeeee, 88 °M 88 [‌888‌]
8 8-MeM8MM8M8 [Me(MM)(eee)]8, MeM 88 eeeeeee, 88 °M 88 [‌888‌]
8 8-MeeMMM8M8 [Me(MM)(eee)]8, MeM 88 eeeeeee, 88 °M 88 [‌888‌]
8 8-eeeeeee [Me(MM)(eee)]8 eeee eeeeeee, 88 °M 88 [‌888‌]
8 8-MMM8M8 MeM, MeM 88 MMM, 88 °M, 88 e 88 [‌888‌]
8 8-MeM≡MM8M8 MeM, MeM 88 MMM, 88 °M, 88 e 88 [‌888‌]
88 8-M8M=MMM8M8 MeM, MeM 88 MMM, 88 °M, 88 e 88 [‌888‌]
88 8-M8MM8M8 MeM, MeM 88 MMM, 88 °M, 88 e 88 [‌888‌]
88 8-MeM8M8 MeM, MeM 88 MMM, 88 °M, 88 e 88 [‌888‌]
88 8-MeM8M8 88/e-MeMM MMM, eeeeee, 88 e 88 [‌888‌]
88 8-(MeMMM8M≡M)M8M8 88/e-MeMM MMM, eeeeee, 88 e 88 [‌888‌]
88 8-MMMM8M8 88/e-MeMM MMM, eeeeee, 88 e 88 [‌888‌]
88 8-MM8M8 88/e-MeMM MMM, eeeeee, 88 e 88 [‌888‌]

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Meeeee 88 Meeeee-Meeeeeeee Meeeeeeeeeeee ee Meeeeeeeee Meeeeeee eeee Meeeee Meeeeee[‌888‌]

Meeeeeeeeee 88

M8 Meeeee (%) Mee
(MM8)8Me 88 [‌888‌]
Me 88 [‌888‌]
(MM8)8Me 88 [‌888‌]

e Meeeeeeeee ee 8M MMM eeeeeeeeeeee.

M eeeeeeeeeeeee eee eeeeeeeeeeeeeee eeeeeeee eeeeeeee eeeeeeee e eeeeee- ee eeeeeeeee-eeeeeeeee eeeee eeeeeeee eeeeeee eeeeeeeeee eeeeeeee eee eeeeee eeeeeee.[‌888‌] Mee eeeeeeeeeeeeee eeeeeeeeee e eeee eee eeeeeeeeee eeeee eeeeeeee eeeeeeee eee eeeeeeeeeeeee. Me eeee eeeeeeee Meeeee’e eeeeeee [Me(η8-MM8)(MMe8)8] ee eeeeeeeeeeee eeeeeeee ee eeeeeeeee eeeeeeeeee eeeeeee eeee eee eeeeeeeeeeeee eeeeeee eeee ee eeeeeeeeeeee eeeeee. Mee eee ee ee ee eeee eeeeeeeee eeeeeeee eeeeeeeee eeee eee eeeeeeee ee eeeeee [Me(MMe8)8(M8)] ee eee(η8-eeeeeeeee-8,8-eeeee)eeeeee(8) [Me(eee)8] eeee eeeeeeeeeeeeeeeeeeeeee ee eeee eeeeeeeee eee eee eeeeeeeeeeeee ee eeeeeeeeee eeeeeee eeee eeeeee eeeeeee. Meeeeeeeeeeee, eee eeeeeeeeeee ee eee eeeeee eeeeeeeee ee eeeeeeeee(MM) eeeeeee ee eeeeeeeeee eee eee eeeeeeeeeeeee ee eeee eeeeeeeeeee eeeeeeee eeeeeeee. Me eeeeeee, eeeeeee, eee eeeeee-eeeee eeeeeeeee eee eeeeeeee ee eeeeeeeee ee eeee eee eeeeee eee eeee eeeeeeee eee eeeee eeee eeeeeeee.

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Meeeee 88 Meeeeeeee ee Meeeeeeee ee Meeeeeeee Meeeeeee Meeeeeeeeee Meeeeeeeeeeee ee e Meeeeeeeee Meeeeee[‌888‌]

Meeeeeeeeeee Meeeeeeee

Meeeeeeeeeeeeee Meeee 88 (Meeee 8, Meeeeee 8–88); Meeeeee Meeeeeeee:[‌888‌]

M eeeeeeeeee ee MeM (8.8 ee, 8.88 eeee), eee(eeeeeeeeeeeeee) eeeeee 88 (8.8 ee, 8.88 eeee), eeeeeeeeeee eeeee (8.8 eeee), eee MeM (8.88 eeee, 88 ee) ee MMM (8.8 eM) eee eeeeeee ee e eeeee eeee (8.8 ee e.e., 88 ee) eeeee ee eeeeeeeeeee eeeeeeee ee MM8 eee eeee eee eeeeee eee eeeeee. Mee eeeeeee eee eeeeee ee 88 °M eee 88 e, eee eeee eee eeeeeeee eee eeeeeeee eeee 8 M ee MMe. Mee eeeeeee eeeee eee eeeeeeeee eeee Me8M (8 ×) eee eee eeeeeeee eeeeeee eee eeeee (MeMM8). Meeee eeeeeee ee eee eeeeeee eeeee eeeeeee eeeeeeee, eee eeeeeee eee eeeeeeee ee eeeeeeeeeeeeee (eeeeee eee, eeeeee/MM8Me8 8:8 ee 8:8 eeeeeeee ee MM8Me8/MeMMe 8:8) ee ee eeeeeee eeeeeeeeee (Me8M/ee MeMMM8 eeee Me8M/ee MMe) eeeeeeee ee eeeeeeeeee eeeeeee eeeeee eee ee eeeeee eeeeeeeeeeeee eeeeeeeeee eeeee 88 eeee eee eeeeee eeeee ee Meeee 8.

References


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