Aryl halides with organometallic

Coupling of aryl halides with organometallic reagents... 

Metallation of alkyl or aryl halides with organometallic compounds... 

Coupling Reactions of Aryl-Alkenyl Halides with Organometallic Reagents and Related Nucleophiles50... 

The general mechanism of coupling reactions of aryl-alkenyl halides with organometallic reagents and nucleophiles is shown in Fig. 9.4. It contains (a) oxidative addition of aryl-alkenyl halides to zero-valent transition metal catalysts such as Pd(0), (b) transmetallation of organometallic reagents to transition metal complexes, and (c) reductive elimination of coupled product with the regeneration of the zero-valent transition metal catalyst. 

Arylation of C-H bonds is achieved by coupling reactions of C-H bonds with aromatic compounds such as halides, triflates, and organometallic reagents. Early works in this field involve the reaction of aryl halides with norbornene. As shown in Scheme 5, the coupling reaction of bromobenzene with norbornene in the presence of Pd(PPh3)4 as a... 

Prim, D. Campagne, J.-M. Joseph, D. Andrioletti, B. Palladium-catalyzed reactions of aryl halides with soft, non-organometallic nucleophiles. Tetrahedron 2002, 58, 2041-2075. 

S. Kozuch, A. Jutand, C. Amatore, S. Shaik, Organometallics 24, 2139 (2005). What Makes for a Good Catalytic Cycle A Theoretical Study of the Role of Anionic Palladium(O) in the Cross-Coupling Reaction of An Aryl Halide with an Anionic Nucleophile. 

Another, mechanistically closely related reaction is the cross-coupling reaction of aryl, benzyl, vinyl, or allyl halides with organometallic coupling reactions, such as Grignard reagents or, preferably, less reducing organometallics such as tin compounds or boronic acids RB(OH)2 the latter allow the reaction to be conducted even in aqueous media.83 The principal reaction steps are ... 

Pd(0) complexes catalyse reactions of aryl halides with various organometallic compounds which lead to biaryls, phenylethenes, ketones, amines and ethers. 

W. J. Considine Alkylation (arylation) of metal halides with organometallics, pp. 4-11 (11). 

The formation of unsymmetric biaryls via catalytic cross-coupling of aryl halides and organometallic compounds has been shown to proceed in ionic liquids with enhanced activity. The Suzuki-Miyaura cross coupling (cf. Section 2.11)... 

Palladium-catalyzed reactions of aryl halides with soft, non-organometallic nucleophiles in the syntheses of heterocycles 02T2041. 

Several chemo-selective aryl-aryl coupling reactions of aromatic halides and organometallics with transition-metal catalysts are known.16 For example, coupling reactions of arylboronic acids with aryl halides with Pd(0) catalyst,17 arylmagnesium halides with aryl halides with Ni(II) catalysts,18 and aryl trialkyl tin compounds with aryl halides with Pd(0) catalyst19 are well known. The polyhalo-aromatic substances were converted into AB -type monomers by selective metallation of one of the halo-functional groups in each monomer. 

Palladium-Catalyzed Reactions of Aryl Halides with Soft, Non-Organometallic Nucleophiles ... 

Mori, M., Chiba, K. and Ban, Y. (1977) The reactions and syntheses with organometallic compounds. V. A new synthesis of indoles and isoquinolines by intramolecular palladium-catalyzed reactions of aryl halides with olefinic bonds. Tetrahedron Lett., 1037-40. 

Kozuch S, Amatore C, Jutand A, Shark S (2005) What makes for a good catalytic cycle A theoretical study of the role of an animiic palladium(O) complex in the cross-coupling of an aryl halide with an anionic nucleophile. Organometallics 24 2319... 

The Sonogashira reaction allows to couple a vinyl or aryl halide with a terminal alkyne. It is probably, together with the Heck reaction, the most spectacular among the coupling methods, because neither of these procedures requires the delicate preparation of an organometallic complex. 

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