Coupling organometallics

Loch, J.A., Albrecht, M., Peris, E. et al. (2002) Palladium complexes with tridentate pincer bis-carbene ligands as efficient catalysts for C-C coupling. Organometallics, 21, 700-6. 

Meyer S, Orben CM, Demeshko S, Dechert S, Meyer F. Synthesis and characterization of di- and tetracarbene iron(II) complexes with chelating N-heterocychc carbene ligands and their apphcation in aryl Grignard-alkyl halide cross-coupling. Organometallics. 2011 30 6692—6702. 

Zhou Y, Zhang WX, Xi Z (2012) 1,3-Butadienylzinctrimer formed via transmetallation from 1,4-dilithio-l,3-butadienes synthesis, structural characterization and application in negishi cross-coupling. Organometallics 31 5546-5550... 

Coupling of Vinyl Phosphonates and Triflates to Organometallic Reagents - vinyl phosphates review Synthesis 1992, 333,... 

Cross coupling of organometallics with organic halides catalyzed by non (ill). 

Some structural aspects of the organometallic compounds of the alkali metals have already been briefly mentioned in Section 4.3.6. The diagonal relation of Li with Mg (p. 76), coupled with the known synthetic utility of Grignard reagents (pp. 132-5), suggests that Li, and perhaps the other alkali metals, might afford synthetically... 

IV-Methylpyrrole with (Cp IrH3)2 and 3,3-dimethyl-1-butene gives a couple of unique organometallic products, 86 and 87 (990M134). In 86, the C—H bond in position 2 is activated and a rare tiVC) ti (C=C) coordination mode is realized. Species 87 is a zwitterionic compound containing a triple bond between the iridium atoms. 

Organometallics in coupling reactions of Tr-deficient azaheterocycles 95AHC(62)305. 

In summary, palladium-mediated reactions, especially cross-coupling reactions have found many applications in quinoline synthesis. It is noteworthy that due to the a and S activation for the C(2) and C(4) positions, even 2-chloro- and 4-chloro-quinolines are viable substrates for palladium-catalyzed reactions under standard conditions. With the advent of the palladium chemistry and more commercially available organometallic substrates, more palladium-mediated quinoline syntheses are to be added to the repertoire of quinoline chemistry. 

Knochel et al. described Pd-catalyzed Negishi cross-coupling reactions between zinc organometallics and aryl iodides in [BMMlM][Bp4]. Scheme 5.2-20 illustrates the reaction for the formation of a 3-substituted cyclohexenone from 3-iodo-2-cyclo-hexen-l-one [82]. 

This organometallic coupling reaction is useful in organic synthesis because it forms carbon-carbon bonds, thereby making possible the preparation of larger molecules from smaller ones. As the following examples indicate, the coupling reaction can be carried out on aryl and vinylic halides as well as on alkyl halides. 

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