Grignard reagents with organic halides

Tamao, K., Sumitani, K., Kumada, M. Seiective carbon-carbon bond formation by cross-coupiing of Grignard reagents with organic halides. Catalysis by nickel-phosphine complexes. J. Am. Chem. Soc. 1972, 94, 4374 376. 

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. 

Tamura, M., Kochi, J. Coupling of Grignard reagents with organic halides. Synthesis 1971, 303-305. 

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. 

The crosscoupling of aryl Grignard reagents with organic halides is generally referred to as Kharasch reaction. See Kharasch MS, Fields EK (1941) J Am Chem Soc 63 2316... 

Survey of Coupling Reactions of Grignard Reagents with Organic Halides... 

SURVEY OF COUPLING REACTIONS OF GRIGNARD REAGENTS WITH ORGANIC HALIDES... 

Before the discovery of the nickel-phosphine catalyst, the cross-coupUng of Grignard reagents with organic halides was seldom used in synthetic practice. This fact was mainly due to the formation of homocoupling products along with significant elimination side reactions. With the use of this new catalyst, the reaction now has wide application in the synthesis of unsymmetrical allca-nes and alkenes. 

The coupling reactions of Grignard reagents with organic halides were described in Chapter 4, and the production of muscopyridine, which is one of the odoriferous constituents of natural musk from the musk deer, by this coupling reaction is also shown in eq. (19.56) [101]. 

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