Kumada cross-coupling reactions, palladium

The Kumada cross-coupling reaction (also occasionally known as the Kharasch cross-coupling reaction) is a nickel- or palladium-catalyzed cross-coupling reaction of a Grignard reagent with an organic halide, triflate, etc. 

Air-stable and readily accessible /f-phosphonate PinP(0)H (231) facilitates highly efficient palladium-catalyzed Kumada cross-coupling reactions of electron-rich as well as electron-poor tosylates, including heteroaromatic electrophiles (Scheme 92). ... 

While the nickel-catalyzed reaction facilitates oxidative addition of substrates problematic to palladium-mediated processes, there is still a great deal of interest in the palladium-catalyzed Kumada cross-coupling reaction due to its enhanced chemoselectivity. Also, as mentioned previously, one distinct advantage of the palladium-catalyzed procedure, is that it allows versatile organolithium reagents to be used as an alternative to Grignard... 

Palladium-catalyzed cross-coupling reaction of organostannanes with organic halides, triflates, etc. For the catalytic cycle, see Kumada coupling on page 345. 

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-... 

One of the first indications that higher valent silanes could be useful donors in palladium-catalyzed cross-coupling reactions was reported by Kumada and Tamao, when they observed that the dipotassium salt of pentafluorosilicate 70 could transfer its vinylphenyl group for the palladium-catalyzed coupling with iodobenzene at high temperature (Scheme 6). ... 

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... 

Hayashi, T., Konishi, M., Kumada, M. Dichloro[1,1 -bis(diphenylphosphino)ferrocene]palladium(ll) an effective catalyst for cross-coupling reaction of a secondary alkyl Grignard reagent with organic halides. Tetrahedron Lett. 1979,1871-1874. 

M. Kumada, Nickel and palladium complex catalyzed cross-coupling reactions of organome-tallic reagents with organic halides, PureAppl. Chem., 52(3), 669-679 (1980). 

Most of the catalytic cross-coupling reactions are based on the activation of a G-F bond of monofluorinated aromatic substrates. The Kumada-Gorriu-, Suzuki-, and Stille-type reactions are catalyzed by nickel or palladium complexes. 

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