Ligand-enabled gold-catalyzed 1,2-heteroarylation of alkenes

Abstract

<p>By adopting the interplay of ligand-enabled Au(I)/Au(III) catalysis and the unique π-activation mode of gold complexes, a highly underscored 1,2-heteroarylation of alkenes has been accomplished. The present ligand-enabled approach not...</p>

π-Alkene/alkyne and carbene complexes of gold(I) stabilized by chelating ligands

“…10,11,12 The hemilabile character of the P^N ligand was shown to promote Au(I)/Au(III) catalysis. 12,15,16,17,18,19,20,21 In addition, in recent parallel studies, our group and Patil's group have highlighted the role of tricoordinate gold(I) alkene complexes in catalytic arylation reactions merging oxidative addition and -activation at gold. 17,19,20 Coordination of the alkene to the gold(I) center was found to occur prior the oxidative addition step, but without preventing it to take place (Scheme 7).…”

“…However, when the metal fragment is activated and preorganized thanks to the use of a chelating ligand, oxidative addition to gold turns easy and general, 10,11,12,13,14 opening new avenues in Au(I)/Au(III) catalysis. 12,15,16,17,18,19,20,21 In this review are discussed the preparation, characterization, structure and reactivity of two types of gold(I) complexes featuring chelating ligands: first, -complexes with alkenes and alkynes side-on coordinated, and then carbene complexes. A small library of chelating ligands of L^L('), L^E (-) ^L and L^X types have been exploited in gold(I) chemistry to date (Figure 2).…”

Fundamental Basis for Implementing Oxidant‐Free Au(I)/Au(III) Catalysis

“…Likewise, the group of Patil also employed the MeDalphos ligand to synthesize 1,2-oxy-and 1,2aminoarylation products from the coupling of aryl iodides with alkenes. [73] In the case of oxyarylations, two-and threecomponent reactions were reported, whereas aminoarylations were only carried out as two-component reactions. The 1,2aminoarylations of alkenes were also shown to proceed by reacting alkenes tethered to aryl iodide moieties with external amines.…”

“…This strategy proved suitable to access products with 5‐, 6‐ and 7‐membered rings and electron‐rich aryl substrates reacted readily. Likewise, the group of Patil also employed the MeDalphos ligand to synthesize 1,2‐oxy‐ and 1,2‐aminoarylation products from the coupling of aryl iodides with alkenes [73] . In the case of oxyarylations, two‐ and three‐component reactions were reported, whereas aminoarylations were only carried out as two‐component reactions.…”

Enantioselective C−H Functionalization Reactions under Gold Catalysis

“…[12] However, the high redox potential of Au(I)/Au(III) couple [54] [E 0 = 1.43 eV] compared to Pd(0)/Pd(II) couple [E 0 = 0.91 eV] renders the oxidative addition pathway extremely difficult for gold-catalyzed processes. Although, the recent literature enjoyed the feasibility of oxidative addition of CÀ X (X=I or Br) bond at Au(I) centre, [55][56][57][58][59][60][61][62][63][64] its extension to far less reactive CÀ H bonds is yet to be realized. As far as σ-bond metathesis is concerned, the viability of such processes in gold catalysis has been shown by Nolan and co-workers for the activation of acidic CÀ H bonds of alkynes, fluorobenzenes, and heteroarenes in the presence of NHC-ligated gold(I) hydroxide complexes.…”