Kumada-Corriu-Tamao Coupling

It was not until Cazin and co-workers introduced the well-defined dimer complex [Pd( J,-Cl)(Cl)(SIPr)]2 that the Kumada-Tamao-Corriu cross-coupling between severely sterically hindered partners was pursued, allowing the synthesis of tri- and tetra-orf/io substituted biaryls [81] (Scheme 6.20). 

Cadiot-Chodkiewicz reaction, 11, 19 Hiyama reaction, 11, 23 Kumada-Tamao-Corriu reaction, 11, 20 Migita-Kosugi-Stille reaction, 11, 12 Negishi coupling, 11, 27 overview, 11, 1-37 Suzuki-Miyaura reaction, 11, 2 terminal alkyne reactions, 11, 15 Cu-mediated reactions acetylenes, 10, 551 dienes, 10, 552... 

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... 

Scheme 3 Kumada-Tamao-Corriu coupling using well-defined Pd-NHC complex 61...

Scheme 8 Kumada-Tamao-Corriu coupling of cyclohexyl magnesium bromide with aryl halides using 75...

Scheme 10 Kumada-Tamao-Corriu coupling of isopropenylmagnesium bromide with aryl bromides catalyzed by [Pd(IPr )(cin)CI] (42)...

Kumada-Tamao-Corriu Cross-Coupling of Aryl Chlorides... 

Scheme 13 Site-selective Kumada-Tamao-Corriu coupling of 2,4-dibromophenol with a Grignard reagent...

Migita-Kosugi-Stille, Negishi-Baba, Mizoroki-Heck, and Kumada-Tamao-Corriu coupling) and for polythiophene synthesis. Direct arylation (see Chapter 4) was highlighted as one of the more efficacious methods. 

Silicon, an element widely used in many facets of organic chemistry [7], was not effectively employed in cross-coupling reactions until 16 years after the first reported transition-metal-catalyzed coupling reactions by Corriu, Kumada, and Tamao [8], Most early developments in this field were achieved by the use of organoboron (1979) [9], organozinc (1977) [10], and organotin (1977) [11] coupling partners (Scheme 7.1). 

The nickel-catalyzed reaction of Grignard reagent with an aryl halide, widely known as Corriu-Kumada-Tamao (CKT), constituted the first example of efficient cross-coupling reaction of aryl halides. However, the elassical protocol was not properly optimized and recent improvements have been achieved using NHC-Ni complexes. 

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