Catalytic Cross Coupling Reactions

For the purpose of an efficient coordination to palladium, Hayashi and Uemura synthesised three bidentate ACTCs [40]. Using 43 as ligand in palladium catalysed cross-coupling reactions between 1-phenyl ethyl zinc chloride 

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Catalytic cross-coupling reactions in synthesis of bihetarenes and arylhetarenes 98T263. 

S. P. Stanforth, Catalytic Cross-Coupling Reactions in Biaryl Synthesis, Tetrahedron 1998, 54, 263-303. 

Hillier AC, Grasa GA, Viciu MS, Lee HM, Yang CL, Nolan SP (2002) Catalytic cross-coupling reactions mediated by palladium/nucleophilic carbene systems. J Qrganomet Chem 653 69-82... 

Stanforth S. P. Catalytic Cross-coupling reactions in biaryl synthesis. Tetrahedron 1998 54 263-303. 

This organolanthanide-catalyzed reaction provides the first example of efficient preparation of well-defined propiolamidines, a new family of amidines which are difficult to access by other means and may show unique reactivity. A wide range of terminal alkynes could be used for this catalytic cross-coupling reaction which was not affected by either electron-withdrawing or -donating substituents or their positions at the phenyl ring of the aromatic alkyne [68]. 

The concept of atom economy has frequently been used to emphasize the minimal number of reactants, as well as selection of low energy starting materials as substrates [7], for example, using substrates that contain a reactive C-H bond rather than a C-X bond. Ideally, a direct catalytic cross-coupling reaction that utilizes traditionally inert C-H bonds would underline this concept as only the loss of nontoxic hydrogen gas or water as by-products would be necessitated (Scheme 3). 

Cross coupling , Acc. Chem. Res. 2008, 41, Special issue (11), 1439-1564 Metal-Catalyzed Cross-Coupling Reactions , 2nd Edn, de Meijere, A. and Diederich, F, Eds., Wiley-VCH, Weinheim, 2004 Catalytic cross-coupling reactions in biaryl synthesis , Stanforth, S. R, Tetrahedron, 1998, 54, 263 Organometallics in coupling reactions in 7t-deficient azaheterocycles , Undheim, K. and Benneche, T.,Adv. Heterocycl Chem., 1995, 62, 305. 

Oxidative addition of aryl (or vinyl) halide to Pd(0) precursor forms the monoarylpalladium complex that is the common intermediate in the catalytic cross-coupling reactions of haloarene with organometallic compounds of main group elements such as Mg, Si, and Sn. Alkynylcopper, formed from alkyne, Cu(I) salt and base in the reaction mixture, transfers the ligand to the above Pd complex, giving an intermediate complex with aryl (or vinyl) and alkynyl ligands bonded to Pd. Reductive elimination of arylacetylene (or enyne) occurs... 

Glassical oxidative addition of a fluorinated alkane at a transition metal center still remains elusive. However, such a step is conceivable in catalytic cross-coupling reactions of primary alkyl fluorides. The reactions of lanthanoid cations with GH3F to form LnF and -GH3 have been described as oxidative additions, but do not conform to our definition of oxidative addition. ... 

Most of the catalytic cross-coupling reactions are based on the activation of a G-F bond of monofluorinated aromatic substrates. The Kumada-Gorriu-, Suzuki-, and Stille-type reactions are catalyzed by nickel or palladium complexes. 

Asymmetric synthesis by the catalytic cross-coupling reaction has been studied most extensively with secondary alkyl Grignard reagents. Asymmetric cross-coupling with... 

Scheme 13.22 Catalytic cross-coupling reactions mediated by a low-valent iron catalyst.

The metal-catalysed C-H bond dual activation and functionalisation have brought in the last two decades a revolution for the direct synthesis of complex molecules and molecular materials. Now the functionalisation of sp C-H bond for cross-coupled C-C or C-heteroatom bond formation presents advantages to replace, with better atom economy, the classical catalytic cross-coupling reactions involving a stoichiometric amount of an organometallic. In parallel the sp C-H bond activation, besides a faster access to natural products, is offering the possibility to functionalise alkanes in connection with renewable energy. 

Based on catalytic cross-coupling reaction between the p-MeCeH4S02Na and p-BrC6H4l, followed by reaction with pyridine, atarget compound containing a motif of 3-3 adrenagic receptor agonist was prepared in 81% yield ... 

Under carefully optimized conditions nickel complexes have shown excellent performance in the catalytic cross-coupling reactions. The possibility of Ni catalysis in Csp -S bond formation was first shown by Cristau et al. in 1981 [15]. The reaction of Ar2S formation was carried out with NiBr2 as a catalyst precursor and o-(Ph2P)2C6H4 as a ligand. The same authors have shown the possibility of the cross-coupling reaction with vinyl halides (Scheme 3.19) [46]. 

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