Alkenes Negishi cross-coupling reaction

W. S. Knowles, R. Noyori, K. B. Sharpless enantioselective catalysis) 2005 Y. Chauvin, R. H. Grubbs, R. R. Schrock (alkene metathesis) 2007 G. Ertl chem. processes on solid surfaces/mechanisms of heterogeneous catalysts) 2010 R. F. Heck, E. Negishi, A. Suzuki Pd Catalyzed cross coupling reactions). 

Negishi, E., Takahashi, T., Baba, S., Van Horn, D. E., Okukado, N. Nickel- or palladium-catalyzed cross coupling. 31. Palladium- or nickel-catalyzed reactions of alkenylmetals with unsaturated organic halides as a selective route to arylated alkenes and conjugated dienes scope, limitations, and mechanism. J. Am. Chem. Soc. 1987,109, 2393-2401. 

The various methods are known as the Stille, Negishi, or Suzuki cross couplings according to whether the organometallic component is a derivative of tin, zinc, or boron, respectively. The Heck reaction accomplishes the same transformation but uses an alkene as the reactant. 

The Pd(0)-catalyzed Heck coupling of alkenes and aryl or alkenyl halides or triflates is one of the most versatile methods for the formation of C C bonds (Scheme 13.2). Notably, Richard F. Heck was jointly awarded the Nobel Prize in Chemistry 2010, with the Japanese chemists Ei-ichi Negishi and Akira Suzuki for palladium-catalyzed cross-couplings in organic synthesis. Although the Heck reaction has been used in organic chemistry since 1968, the synthetic potential of this transformation has been proven after many years. ... 

Carbon-heteroatom double bonds can also participate in this reaction. These include both carbonyl compounds (Scheme 11.37) and imines (Scheme 11.38). Addition to aldehydes is co-catalysed by tin(II) or indium(III) salts. Under these conditions, tetrahydrofiirans are obtained. The presence or absence of the co-catalyst can also switch the reaction from one mode to another (Scheme 11.39). An indium cocatalysed cycloaddition to a 7-pyrone aldehyde 11.117 was used in a synthesis of aureothin 11.122 and A-acetylaureothamine 11.123 (Scheme 11.40). Cross-metathesis of the exo-cyc ic alkene 11.118 allowed a subsequent Suzuki coupling with a gem-dibromide 11.120 that showed the expected selectivity (Section 2.1.4.2). This reaction required the use of thallium ethoxide as the Lewis base to suppress the formation of side products. A Negishi coupling completed the synthesis of aureothin 11.122. Reduction and acylation of the nitro group yielded A-acetylaureothamine 11.123. The latter compound is active digainst Helicobacter pylori, a bacterium behind stomach ulcers. 

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