Catalytic CC.pdfVIP

Minireviews F. Monnier and M. Taillefer DOI: 10.1002/anie.座机电话号码7 Coupling Reactions Catalytic C C, C N, and C O Ullmann-Type Coupling Reactions Florian Monnier* and Marc Taillefer* arylation · catalysis · copper · cross-coupling · nucleophiles Copper-catalyzed Ullmann condensations are key reactions for the formation of carbon–heteroatom and carbon–carbon bonds in organic synthesis. These reactions can lead to structural moieties that are prevalent in building blocks of active molecules in the life sciences and in many material precursors. An increasing number of publications have appeared concerning Ullmann-type intermolecular reactions for the coupling of aryl and vinyl halides with N, O, and C nucleophiles, [11] preferentially used. However, some and this Minireview highlights recent and major developments in this reported studies had revealed rate topic since 2004. enhancements when the arylations were conducted in the presence of ligands for the copper center or of 1. Introduction other additives.[12] These latter com- pounds were thought to increase the catalyst solubility or The copper-mediated arylation of amines,[1] phenols[2] stability and/or prevent aggregation of the metal, but their Ullmann condensations , amides, carbamates[3] Ullmann– exact role was not established unequivocally. Goldberg condensations , and activated methylene com- Finally in 2001, two research groups achieved important pounds[4] Ullmann–Hurtley condensations are well-docu- breakthroughs[13] with the discovery of versatile and very mented methods that were discovered several decades before efficient new copper/ligand systems for the formation of CC, the palladium- and nickel-catalyzed procedures. For more C N, and C O bonds that enabled the use of only catalytic than a century they were some of the most useful and amounts of metal under much milder conditions 90–110 8C . pra