Halides nickel-catalyzed coupling with Grignard

In the area of organometallic chemistry, we begin with a procedure for the palladium-catalyzed animation of aryl halides and aryl triflates, illustrated by syntheses of N-HEXYL-2-METHYL-4-METHOXYANIUNE and N-METHYL-N-<4-CHLOROPHENYL)-ANILINE. The next procedure describes the synthesis of 1,2,3,4-TETRAHYDROCARBAZOLE by the palladium-catalyzed annulation of ketones with o-iodoaniline. Next, a procedure for the synthesis of 2,7-DIMETHYLNAPHTHALENE via the nickel-catalyzed coupling of aryl O-carbamates with Grignard reagents is presented. The fourth procedure in this section describes the synthesis of 5-METHYL-2,2 -BIPYRIDINE by a Negishi cross-coupling reaction... 

A genuine coupling based on a group 10 M(11)/M(1V) catalysis is probably involved in the nickel-catalyzed coupling of alkyl halides and tosylates with the Grignard reagents discovered by Kambe (Scheme 1.22) [206]. A similar system has... 

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. 

Nickel(II) salts are able to catalyze the coupling of Grignard reagents with alkenyl and aryl halides. A soluble 6 -phosphine complex, Ni(dppe)2Cl2, is a particularly effective catalyst.266 The main distinction between this reaction and Pd-catalyzed cross... 

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]. 

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. ... 

Selective cross-coupling reactions between C(sp ) and C(5p ) centers had been one of the most difficult tasks in carbon-carbon bond synthesis until the early 1970s, when it was first reported that iron, nickel, palladium and copper - catalysts are extremely effective for cross-coupling of Grignard reagents with organic halides. Now, nearly 20 years later, transition metal catalyz cross-coupling has become the reaction of first choice for this purpose. 

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