Gold‐Catalyzed Allylation of Aryl Boronic Acids: Accessing Cross‐Coupling Reactivity with Gold

Abstract

A sp3 – sp2 C-C cross-coupling reaction catalyzed by gold in the absence of a sacrificial oxidant is described. Vital to the success of this method is the implementation of a bimetallic catalyst bearing a bis(phosphino)amine ligand. A mechanistic hypothesis is presented, and observable transmetallation, C-Br oxidative addition, and C-C reductive elimination in a model gold complex are shown. We expect that this method will serve as a platform for the development of novel transformations involving redox-active gold catalysts.

Oxidative Addition of Carbon–Carbon Bonds to Gold

“…Reductive eliminations of C À C bonds from square-planar complexes are common in organometallic chemistry, but very rare with gold and so far limited to C(aryl) À C(aryl) bond formation. [19][20][21] In conclusion, the oxidative addition of CÀC bonds to gold was disclosed. Bent gold(I) complexes [(DPCb)Au] + readily insert into the four-membered rings of biphenylene and benzocyclobutenone.…”

Fundamental Elementary Steps in Gold Chemistry

“…Allyl bromides and arylboronic acids were reacted in the presence of mononuclear or dinuclear gold(I) chloride complexes to give allylated arenes (Scheme 3.75) [182].…”

Phosphino‐amine (PN) Ligands for Rapid Catalyst Discovery in Ruthenium‐Catalyzed Hydrogen‐Borrowing Alkylation of Anilines: A Proof of Principle

“…[3,4] Indeed, ligands based on the PN scaffold have been widely used in catalytic processes, including nitrile hydrations, [5] transfer hydrogenations of acetophenone derivatives [6] and cross-coupling reactions with gold. [7] Many enantioselective catalytic processes also benefit from the modular chiral P-N systems pioneered by Alexakis and Feringa. [8] In bulk processes, the use of PNP ligands is the basis for industrial chromium-based production of 1-hexene and, more recently, 1-octene from ethene.…”