DUGi

Oxidant-Free Au(I)-Catalyzed Halide Exchange and Csp2-O Bond Forming Reactions

http://dugi.udg.edu/item/http:@@@@hdl.handle.net@@2072@@297433

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

This work was supported by grants from the European Research Council (Starting Grant Project ERC-2011-StG-277801), the Spanish MINECO (CTQ2013-43012-P, Consolider-Ingenio CSD2010-00065, INNPLANTA project INP-2011-0059-PCT- 420000-ACT1) and Generalitat de Catalunya (2014 SGR 862)

American Chemical Society (ACS)