1329710-02-2Relevant articles and documents
Oxidant-Free Au(I)-Catalyzed Halide Exchange and Csp2-O Bond Forming Reactions
Serra, Jordi,Whiteoak, Christopher J.,Acu?a-Parés, Ferran,Font, Marc,Luis, Josep M.,Lloret-Fillol, Julio,Ribas, Xavi
, p. 13389 - 13397 (2015/11/09)
Au has been demonstrated to mediate a number of organic transformations through the utilization of its π Lewis acid character, Au(I)/Au(III) redox properties or a combination of both. As a result of the high oxidation potential of the Au(I)/Au(III) couple, redox catalysis involving Au typically requires the use of a strong external oxidant. This study demonstrates unusual external oxidant-free Au(I)-catalyzed halide exchange (including fluorination) and Csp2-O bond formation reactions utilizing a model aryl halide macrocyclic substrate. Additionally, the halide exchange and Csp2-O coupling reactivity could also be extrapolated to substrates bearing a single chelating group, providing further insight into the reaction mechanism. This work provides the first examples of external oxidant-free Au(I)-catalyzed carbon-heteroatom cross-coupling reactions.
Aryl-O reductive elimination from reaction of well-defined aryl-Cu III species with phenolates: The importance of ligand reactivity
Casitas, Alicia,Ioannidis, Nikolaos,Mitrikas, George,Costas, Miquel,Ribas, Xavi
supporting information; experimental part, p. 8796 - 8799 (2011/10/17)
Well-defined aryl-Cuiii species undergo rapid reductive elimination upon reaction with phenolates (PhO-), to form aryl-OPh cross-coupling products. Kinetic studies show that the reaction follows a different mechanistic pathway compared to the reaction with phenols. The pH active cyclized pincer-like ligand undergoes an initial amine deprotonation that triggers a faster reactivity at room temperature. A mechanistic proposal for the enhanced reactivity and the role of EPR-detected Cuii species will be discussed in detail. The Royal Society of Chemistry 2011.
