Oxidative additions of alkynyl/vinyl iodides to gold and gold-catalyzed vinylation reactions triggered by the MeDalphos ligand

Abstract

The hemilabile Ad2P(o-C6H4)NMe2 ligand promotes fast, quantitative and irreversible oxidative addition of alkynyl and vinyl iodides to gold. The reaction is general. It works with a broad range of substrates...

Hemilabile MIC^N ligands allow oxidant-free Au(i)/Au(iii) arylation-lactonization of γ-alkenoic acids

“…1–6 On the other hand, redox Au( i )/Au( iii ) catalysis has been less explored and mainly achieved in the presence of sacrificial external oxidants, 7–17 especially due to the reluctance of Au( i ) to undergo oxidative addition. 18–21 In this regard, several strategies have been explored to overcome this limitation, 22–46 among which the chelation-assisted strategy in pre-designed ligands 30–34 or the oxidative addition using strained molecules such as biphenylene stand out. 35 Bourissou pioneered in 2014 the intramolecular oxidative addition of C sp 2 –X bonds (X = Br, I) at Au( i ) by utilizing rigid 8-halonaphthyl phosphine model substrates, which suitably place the C sp 2 –X bond close to the Au( i ) atom upon coordination to the phosphine moiety.…”

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.…”

Inverted Ligand Field in a Pentanuclear Bow Tie Au/Fe Carbonyl Cluster

“…For many years, the development of homogeneous gold-based catalysts − has been hampered due to the slight recalcitrance of gold complexes to undergo the most common processes of coordination chemistry, such as oxidative addition and reductive elimination. , Only in recent years has gold chemistry experienced a renewed interest made possible by the ubiquitous employment of both gold complexes and nanoparticles in nanomedicine, − sensors, , and catalysis − as well as environmental applications . Moreover, in many catalytic cycles, the involvement of Au­(III) intermediates is suggested. − …”