Au-Catalyzed Cross-Coupling of Arenes via Double C–H Activation

Abstract

The first methodology for Au(I/III)-catalyzed oxidative cross-coupling of arenes via double C-H activation has been developed. The reaction is fully selective for the cross-coupling between electron-rich hetero-/carbocyclic arenes and electron-poor arenes bearing relatively acidic C-H bonds. The inherently high cross-selectivity of the system obviates the need for directing groups or a large excess of one of the coupling partners.

Intramolecular dehydrogenative coupling of biaryl tertiary amines promoted with t-BuOK/DMF: A convenient synthesis of 6-aryl-5,6-dihydrophenanthridines

“…[1][2][3][4][5][6][7][8][9][10] This strategy, introduced by Li and other researchers, is demonstrated to be a superior alternative to classic coupling procedures using prefunctionalized starting materials. CDC reactions are generally achieved in the presence of transition-metal catalysts and sacrificial oxidants or Hacceptors.…”

Gold‐Catalyzed Direct Oxidative Arylation with Boron Coupling Partners

“…Anisoles (6, 7), including halogen-containing ones (8)(9)(10)(11), underwent the reaction with complete site selectivity,a lso highlighting the functional-group compatibility and orthogonality of this method compared to classical cross-coupling reactions.X -Ray diffraction analysis of 9 confirmed the bond formation at the para position of the electron-rich arene. Anisoles (6, 7), including halogen-containing ones (8)(9)(10)(11), underwent the reaction with complete site selectivity,a lso highlighting the functional-group compatibility and orthogonality of this method compared to classical cross-coupling reactions.X -Ray diffraction analysis of 9 confirmed the bond formation at the para position of the electron-rich arene.…”

“…[12] Control experiments to establish the reaction mechanism were designed next. Moreover,unlike the previously reported silver-promoted transfer of electron-deficient arenes to gold, [10,16] no other additives were required for as uccessful 1P in [b] PhI ( Scheme 2. Asimilar result was obtained in the presence of two equivalents of p-xylene,w hich does not seem to interfere with the B/Au I transmetalation process.No reaction was detected with Ph 3 PAuCl, thus signalling the low reactivity of chloride in this B/Au I exchange (entry 2).…”

“…[7,10] Thec ompetitive arylation of 1,3-dimethoxy-benzene with two different electron-deficient aryl silanes and boronates under the standard reaction conditions of Table 1p roduced 88 %y ield of the heterocoupling product 27,s temming from the boronic ester while no reactivity with the arylsilane was observed (Scheme 5). [7,10] Thec ompetitive arylation of 1,3-dimethoxy-benzene with two different electron-deficient aryl silanes and boronates under the standard reaction conditions of Table 1p roduced 88 %y ield of the heterocoupling product 27,s temming from the boronic ester while no reactivity with the arylsilane was observed (Scheme 5).…”

Photoredox‐Controlled Mono‐ and Di‐Multifluoroarylation of C(sp3)−H Bonds with Aryl Fluorides

“…[22] Multifluoroaryl motifs are known to undergo hydrodefluorination to afford partially fluorinated aromatic compounds. As cale-up to 7mmol did not compromise the efficiency (85 %).…”