Negishi cross-coupling reactions, palladium chemistry

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... 

Negishi E, Tan Z (2005) Diastereoselective, Enantioselective, and Regioselective Carbo-alumination Reactions Catalyzed by Zirconocene Derivatives. 8 139-176 Netherton M, Fu GC (2005)Palladium-catalyzed Cross-Coupling Reactions of Unactivated Alkyl Electrophiles with Organometallic Compounds. 14 85-108 NicolaouKC, KingNP, He Y (1998) Ring-Closing Metathesis in the Synthesis of EpothUones and Polyether Natural Products. 1 73-104 Nishiyama H (2004) Cyclopropanation with Ruthenium Catalysts. 11 81-92 Noels A, Demonceau A, Delaude L (2004) Ruthenium Promoted Catalysed Radical Processes toward Fine Chemistry. 11 155-171... 

Robert F. Heck shared the 2010 Nobel Prize in Chemistry with Ei-iohi Negishi and Akira Suzuki for development of palladium-catalyzed cross coupling reactions. 

As a final comment, although restricted in its essence to palladium chemistry - but which is nonetheless at the heart of modern cross-coupling arylation reactions - we quote from Astruc [12i], in conclusion, the field of palladium-catalyzed cross-coupling reactions for their work in which Heck, Negishi, and Suzuki were awarded the 2010 Nobel Prize in chemistry is extremely rich and productive and will continue to grow with major synthetic applications and green implications in the future. ... 

Based on an early finding, the cross-coupling reaction of zinc reagents with organyl halides is now one of the mostly used palladium-catalyzed reactions. Discovered by the Negishi group over 35 years ago, they also extensively explored the seope and the limitations of this very useful reaction. This chemistry has extensively being... 

Negishi, E.-i. Palladium-catalyzed cross-coupling involving 3-hetero-substituted compounds. Palladium-catalyzed a-substitution reactions of enolates and related derivatives other than the Tsuji-Trost allylation reaction. Handbook of Organopalladium Chemistry for Organic Synthesis 2002, 1, 693-719. 

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