Biaryls and heterobiaryls

Chamoin S, Houldsworth S, Kruse CG, Bakker WI, Snieckus V. The Suzuki-Miyaura cross coupling reactions on solid support. Link to solution phase directed ortho metalation. The Leznoff acetal linker approach to biaryl and heterobiaryl aldehydes. Tetrahedron Lett 1998 39 4179-4182. 

Thienylboronic acids are useful building blocks for preparing biaryls and heterobiaryls employing the Suzuki reaction. In one case, a Suzuki coupling between thiophene-3-boronic... 

Palladium chemistry, despite its immaturity, has rapidly become an indispensable tool for synthetic organic chemists. Today, palladium-catalyzed coupling is the method of choice for the synthesis of a wide range of biaryls and heterobiaryls. The number of applications of palladium chemistry to the syntheses of heterocycles has grown exponentially. 

Chamoin, S. Houldsworth, S. Snieckus, V. The Stille Cross Coupling Reactions on Solid Support. Link to Solution Phase Directed ortho Metala-tion. An Ester Linker Approach to Styryl, Biaryl and Heterobiaryl Carboxylic Acids, Tetrahedron Lett. 1998, 39, 4175-4178. 

Anctil, E. J.-G. Snieckus, V. The directed ortho metalation-cross coupling symbiosis. Regioselective methodologies for biaryls and heterobiaryls. Deployment in aromatic and hetero-... 

Thienylboronic acids are useful building blocks for preparing biaryls and heterobiaryls employing the Suzuki reaction. In one case, a Suzuki coupling between thiophene-3-boronic acid and iodocyclopropane 99 was promoted by cesium fluoride to furnish the adduct 100 with retention of configuration [74]. In another example, the union between thiophene-3-boronic acid and 5-bromo-2,2-dimethoxy-l,3-mdandione (101) provided ninhydrin derivative 102 [75]. 

Miyaura cross-couplings to yield biaryl and heterobiaryl aldehydes as products [79]. 

In 2010, Organ and co-workers investigated the activity of Pd-PEPPSI-IPr (27) and Pd-PEPPSI-IPent (29) in the synthesis of di-, tri-, and tetra-ort/io-substituted biaryl and heterobiaryl products. With a few exceptions, 29 was found to be the optimal pre-catalyst system, generating various biaryl and heterobiaryl products possessing a variety of functional groups and/or orf/io-substituents (Scheme 29). In particular, a number of tetra-ort/jo-substituted biaryl compounds were synthesized in excellent... 

By the same procedure differently substituted aryl halides can also be coupled to biaryls and heterobiaryls but the method is rather impractical because the desired unsymmetrical product is always accompanied by the symmetrical ones. 

Regioselective ortho metalation-cross coupling for biaryls and heterobiaryls in aromatic and heteroaromatic natural product s)mthesis 02JOM(653)150. 

With the application of copper(I)-thiophene-2-carboxylate (CuTC 76), Liebeskind was able to access substituted biaryls and heterobiaryls at room temperature [73]. The thiophene derivative serves as ligating substituent (Eq. 12.18-1, Scheme 12.18) and mediates the formation of the required aryl copper species. An intramolecular example of such a CuTC-promoted Ullmann reaction in the preparation of tricycle 80 is outlined in Equation 12.18-2, Scheme 12.18. 

Furthermore, medicinally relevant biaryls and heterobiaryls (Figure 5-14) like cystine,PDE472, xenalipin, tasosartan, and valsartan, were constructed via Negishi cross-coupling reactions. ... 

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