Corriu-Kumada cross-coupling reactions

Because of the extraordinary strength of the carbon-fluorine bond, transition metal-mediated activation of fluoroalkanes and arenes is not easy to achieve. Nevertheless, activation of the C-F bond in highly electron-deficient compounds such as 2,4,6-trifluoropyrimidine, pentafluoropyridine, or hexafluorobenzene is possible with stoichiometric amounts of bis(triethylphosphano) nickel(O) [101] (Scheme 2.45). More recently Herrmann and coworkers [102] have described a variant of the Kumada-Corriu cross-coupling reaction [103] between fluorobenzene and aryl Grignard compounds which uses catalytic amounts of nickel carbene complexes. Hammett analysis of the relative kinetic rate constants indicated that the reaction proceeds via initial oxidative addition of the fluoroaromatic reactant to the nickel(O) species. 

Scheme 14.10 The combined Suzuki-Miyaura or Kumada-Corriu cross-coupling reactions for the synthesis of polysubstituted aromatics.

Table 14,9 Selected DoM-Kumada-Corriu cross-coupling reactions forming Ar-Ar systems.

Scheme 1.12 (a) General conditions for the Tamao-Kumada-Corriu cross-coupling reaction, (b) The proposed mechanism for the Tamao-Kumada-Corriu cross-coupling arylation procedure (note the base used is an alkoxide or hydroxide) [12a]. 

Scheme 1.13 The enantioselective catalytic variant of the Tamao-Kumada-Corriu cross-coupling reaction as developed by Hayashi et al. [30].

Tamao-Kumada-Corriu Cross-Coupling Reaction... 

A cross-coupling arylation procedure was developed independently in 1972 by Tamao and Kumada in Japan and Corriu in France and is known as the Tamao-Kumada-Corriu cross-rxtupling reaction... 

Other successful examples of catalysts containing NHC ligands are found in palladium- and nickel-catalyzed carbon-carbon bond formations. The catalyst development with these metals has focused in particular on Heck-type reactions, especially the Mizoroki-Heck reaction itself [Eq. (42)] and various cross coupling reactions [Eq. (43)], e.g., the Suzuki-Miyaura reaction ([M] = and the Kumada-Corriu reaction ([M] = MgBr). " Related reactions like the Sonogashira coupling [Eq. (44)]326-329 Buchwald-... 

In 1971, a year before the groups of Corriu and Kumada [5] independently reported the groundbreaking work on the topic of nickel-catalyzed cross-coupling reactions of aryl and vinyl halides with Grignard reagents, Tamura and Kochi described an iron-catalyzed vinylation reaction of Grignard reagents with vinyl halides (Scheme 5.1) [6]. 

Since the discovery of transistion metal-catalyzed cross-coupling reactions by the groups of Kochi, Kumada and Corriu in the early 1970s, impressive progress has been achieved in the development of these methods into a synthetically indispensable... 

Cross-coupling reactions 5-alkenylboron boron compounds, 9, 208 with alkenylpalladium(II) complexes, 8, 280 5-alkylboron boron, 9, 206 in alkyne C-H activations, 10, 157 5-alkynylboron compounds, 9, 212 5-allylboron compounds, 9, 212 allystannanes, 3, 840 for aryl and alkenyl ethers via copper catalysts, 10, 650 via palladium catalysts, 10, 654 5-arylboron boron compounds, 9, 208 with bis(alkoxide)titanium alkyne complexes, 4, 276 carbonyls and imines, 11, 66 in catalytic C-F activation, 1, 737, 1, 748 for C-C bond formation Cadiot-Chodkiewicz reaction, 11, 19 Hiyama reaction, 11, 23 Kumada-Tamao-Corriu reaction, 11, 20 via Migita-Kosugi-Stille reaction, 11, 12 Negishi coupling, 11, 27 overview, 11, 1-37 via Suzuki-Miyaura reaction, 11, 2 terminal alkyne reactions, 11, 15 for C-H activation, 10, 116-117 for C-N bonds via amination, 10, 706 diborons, 9, 167... 

After Kumada and Tamao and Corriu independently reported the nickel(II) salts-and complexes-catalyzed cross-coupling reaction of Grignard reagents with aryl and alkenyl halides, the Pd-catalyzed reaction of Grignard reagents was first reported by Murahashi. ... 

While organic chlorides, bromides, and iodides are still the most common substrates, recently the scope has been expanded to include organic fluorides, nitriles, ethers, triflates, phosphates, iodonium salts, and substrates with various chalconide-leaving groups. Of the different cross-coupling reactions covered in this article, the Kumada Corriu protocol has been the least reviewed. However, the topic has been covered in recent historical treatments. ... 

Discoveries made in the late 1970s of electrical conductivity in conjugated polymers spawned a monumental interest in the study of these materials, which are ideally suited for synthesis via cross-coupling reactions. Yamamoto was the first to realize this possibility with a regiochemicahy defined synthesis of poly(/ -phenylene) formed via the Kumada-Corriu protocol. Since then, various cross-coupling reactions have been applied in condensation polymerization reactions,with the Suzuki and Sonogashira protocols gaining the most widespread use. 

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