Kumada reaction

Nickel (II) Catalyzed Cross-Coupling with Grignard Reagents (Kumada Reaction) Pure AppJ. Chem. 1980, 52, 669 Bull Chern. Soc.Jpn. 1976, 49, 1958... 

CROSS-COUPLING OF ARYLCHLORIDES WITH ARYL GRIGNARD REAGENTS (KUMADA REACTION)... 

Organomagnesium reagents, which can serve as the nucleophiles in the Kumada coupling, are easy to make and many of them are commercially available. Even though some Kumada reactions can be run at room or lower temperature, many functional groups are not tolerant of Grignard reagents. Nonetheless, in the synthesis of thienylbenzoic acid 24, the carboxylic acid moiety did survive the reaction conditions [25],... 

Phan, N T S. and Brown, D.H. and Styring, P. (2004). A faeile method for catalyst immobilisation on silica nickel catalysed Kumada reactions in mini-continuous flow and batch reactors. Green Chemistry, 6, 526-532. 

Huang, J. Nolan, S. P. Efficient cross-coupling of aryl chlorides with aryl Grignard reagents (Kumada reaction) mediated by a Pd/imidazolium chloride system./. Am. 

MW, 175 °C, 10 min Scheme 74 Kumada reaction with aryl chlorides... 

Based on these results, conditions for alkyl-Sonogashira coupling reactions were developed. Primary alkyl halides reacted with terminal alkynes catalyzed by 5 mol% of complex 24a and Cul in the presence of substoichiometric amounts of Nal for bromides or Bu4NI for alkyl chlorides (entry 29) [73]. The latter serves to catalyze the in situ generation of more reactive alkyl iodides under the reaction conditions. The internal alkyne products were isolated in 57-89% yield. The Sonogashira coupling can also be combined to the Kumada reaction described above. a,o)-Chloroalkyl bromides underwent the Kumada coupling first selectively... 

Kumada reactions. Polyfunctional pyridines can be prepared by Pd(0)-catalyzed cross-coupling of functionalized arylmagnesium halides with chloro- or bromopyridines at temperatures as low as 40 C, e.g., Scheme 114... 

Chapter 5 includes complete coverage of the transition metals-mediated carbon-carbon bond forming reactions. Pd-, Ni-, Cr-, Zr- and Cu-catalyzed reactions such as Heck, Negishi, Sonogashira, Suzuki, Hiyama, Stille, Kumada reactions are covered in adequate details including the applications of these reactions in organic synthesis. 

Huang, J., Nolan, S. P. Efficient Cross-Coupling of Aryl Chlorides with Aryl Grignard Reagents (Kumada Reaction) Mediated by a Palladium/lmidazolium Chloride System. J. Am. Chem. Soc. 1999, 121,9889-9890. 

The Kumada reaction has been used for the preparation of polyfunctionalized pyridines. In one example, Grignard reagent 82 was coupled to pyridyl derivative 81 using palladium catalysis to afford 83 in excellent yield [28]. 

The Grignard reagent of 2-chloro thiophene underwent the Kumada reaction with 2,6-dichloropyridine 84 to produce the monosubstituted pyridine 85. Mixed heteroarene 86 was afforded when 85 was allowed to react with the Grignard derived from, V-methyl-2-bromoindole [29]. 

The bis(organomagnesium) reagent 87 was allowed to undergo a Kumada reaction with the dibromopyridine 40 to afford 88, an example of a poly(phenylenepyridine) [30]. 

Kumada reactions can be run at ambient temperature or lower, many functional groups... 

The following Tables 14.1-14.5 present a list of recent catalyst developments for the Heck, Suzuki, Suzuki-Miyaura, Sonogashira, Negishi, and Kumada reactions. 

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