Aryl halides, Negishi reaction

Unlike normal all-carbon aryl halides, regioselective Negishi coupling reaction of 2,3-dibromofuran 27 with 2-furylzinc chloride was achieved at C(2) to afford bisfuran 28 [35]. 

Negishi and co-workers also reported in 1978 Pd-catalyzed alkynylation reactions with alkynylmetals containing Mg, B, A1 and Sn. But B and Sn versions have sometimes been known as the Suzuki and Stille alkynylation reactions, respectively. Negishi and co-workers during 1977-1978 reported the Pd-catalyzed alkynylation reactions of alkynylzinc reagents with 1-halo-l-alkynes and aryl halides. 

The Negishi reaction, which couples aryl and vinyl halides with organozinc reagents, is potentially more usefiil than... 

J. F. Hartwig, Palladium-Catalyzed Amination of Aryl Halides and Related Reactions, in Handbook of Organopalladium Chemistry for Organic Synthesis , ed. E. Negishi, John Wiley Sons, Hoboken, NJ, 2002, p. 1051. 

Negishi, E., Baba, S. Novel stereoselective alkenyl-aryl coupling via nickel-catalyzed reaction of alkenylalanes with aryl halides. J. Chem. Soc., Chem, Commun, 1976, 596-597. 

Negishi, E., King, A. O., Okukado, N. Selective carbon-carbon bond formation via transition metal catalysis. 3. A highly selective synthesis of unsymmetrical biaryls and diarylmethanes by the nickel- or palladium-catalyzed reaction of aryl- and benzylzinc derivatives with aryl halides. J. Org. Chem. 1977,42, 1821-1823. 

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... 

Fiuylzinc halides also undergo coupling with vinyl and aryl tellurides in a variation of the Negishi reaction. In one example, Z-vinylic telluride 35 reacts with 2-furylzinc chloride to furnish 2-vinylfuran 36 in 75% yield [47]. 

Unlike normal all-carbon aryl halides, regioselective Negishi couplings of dihalofu-rans and trihalobenzofurans are synthetically useful. Bach and coworkers have studied both systems extensively and use a variety of cross-coupling reactions to produce functionalized furans and benzofurans. In one example of a selective Negishi reaction,... 

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