ChemInform Abstract: Biaryls in Nature: A Multi‐Facetted Class of Stereochemically, Biosynthetically, and Pharmacologically Intriguing Secondary Metabolites

Bringmann, Gerhard; Guenther, Christian; Ochse, Michael; Schupp, O.; Tasler, Stefan

doi:10.1002/chin.200217291

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“…Synthesis of biaryls is an important transformation in synthetic organic chemistry because biaryls are key building blocks for a large number of natural products, biologically significant agrochemicals, and pharmaceuticals . Moreover, biaryls can also be used as chiral ligands, monomers for conductive polymers, and precursors for rigid liquid crystals. , Traditionally, the symmetrical biaryls are synthesized by the copper-mediated Ullmann reductive homocoupling of aromatic halides .…”

Section: Introductionmentioning

confidence: 99%

Palladium-Catalyzed Reductive Homocoupling of Aromatic Halides and Oxidation of Alcohols

Zeng

Shao

et al. 2010

J. Org. Chem.

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Palladium-catalyzed reductive homocoupling of aromatic halides can be performed in alcohol solutions without any auxiliary reducing reagents. Pd(dppf)Cl(2) [dppf = 1,1'-bis(diphenylphosphino)ferrocene] has been shown as the most effective catalyst among the palladium catalysts screened for the model reductive homocoupling of iodobenzene in alcoholic solutions. The reduction of iodobenzene is stoichiometrically coupled with the oxidation of solvent alcohol (3-pentanol). The X-ray photoelectron spectroscopic (XPS) studies clearly indicate that the oxidation of solvent alcohol molecules is involved with the in situ regeneration of the reductive Pd(0)(dppf) active species, indicating that the solvent alcohol also reacts as a reducing reagent for the reductive homocoupling of aromatic halides. Elimination of the external reducing reagents will simplify the product separation and purification. Base is essential for the success of the Pd(dppf)Cl(2)-catalyzed redox reaction as 2 molar equiv of base is needed to neutralize the acid byproduct formed. Biaryls are the predominant products for the Pd(dppf)Cl(2)-catalyzed reductions of the unsubstituted aromatic halides in 3-pentanol solution, whereas the dehalogenation products are predominant for the Pd(dppf)Cl(2)-catalyzed reductions of the substituted aromatic halides. The reaction mechanisms have been discussed for the palladium-mediated concomitant reduction of aromatic halides and oxidation of alcohols without any auxiliary reductants and oxidants.

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Section: Introductionmentioning

confidence: 99%