Redox‐Controlled Selectivity of CH Activation in the Oxidative Cross‐Coupling of Arenes

Abstract

Gold brings us together: Taking advantage of the orthogonal reactivities of AuI and AuIII towards CH activation of electron‐poor and electron‐rich arenes, respectively, a novel approach for the synthesis of biaryls through double CH activation is proposed. Stoichiometric studies demonstrate that these oxidative couplings occur with high selectivity at low temperature.

Early–Late Heterometallic Complexes of Gold and Zirconium: Photoluminescence and Reactivity

“…In the 31 P{ 1 H} NMR spectra, a singlet at 23.3 ppm is observed for 6 , whereas a pseudo‐quintet is seen at 34.4 ppm (with a coupling constant of 8.8 Hz) for 7 . The signal splitting is caused by long‐range coupling to the fluorine atoms of the C 6 F 5 ligands, and this can also be observed in comparable compounds . In the 19 F{ 1 H} NMR spectrum, a characteristic set of signals, with an integration ratio of 2:1:2 for the C 6 F 5 groups, is observed at −116.1 ppm ( ortho ‐ F ), −158.8 ppm ( 3 J FF =20.4 Hz, para ‐ F ) and −162.3 ppm ( meta‐F ), respectively.…”

Fundamental Elementary Steps in Gold Chemistry

“…A related cross-coupling reaction of two different arenes was established by Larrosa and coworkers [181], though stoichiometric in gold. Based on the orthogonal reactivity of Au(I)/(Au(III) complexes towards CH activation of electron-poor/electron-rich arenes, respectively (see Sect.…”

Self-control tames the coupling of reactive radicals

“…eq 5). 32 Although thtAuBr3 itself does not react with either coupling partner, formation of an active Au(III) species under catalytically-relevant conditions, and its reactivity towards arylsilanes, was confirmed by treating the precatalyst with C6D5I(OH)OMs in the presence of arylsilane 13 (Scheme 4B). Addition of excess […”