Bis(μ-iodo)bis[(−)-sparteine]dicopper: A Versatile Catalyst for Direct O-Arylation and O-Alkylation of Phenols and Aliphatic Alcohols with Haloarenes

Abstract

The easy to prepare dimeric bis(μ-iodo)bis[(−)-sparteine]dicopper ([CuI{(−)-spa}]2 complex) is shown to be versatile catalyst for O-arylation and O-alkylation with various aryl halides with phenols and aliphatic alcohols respectively, including less reactive aryl chlorides, such as chlorobenzene under mild conditions.

Mild and General Palladium-Catalyzed Synthesis of Methyl Aryl Ethers Enabled by the Use of a Palladacycle Precatalyst

“…In addition, copper-catalyzed coupling of methanol with aryl iodides also serves as a convenient method to prepare anisoles. 15 Despite these advances, the substrate scope is generally limited to aryl halides and halopyridines. Moreover, a relatively high temperature (≥ 70 °C) is usually required.…”

“…In 2012, Beller and Peruncheralathan reported a more general Pd-catalyzed coupling of methanol and methanol- d 4 with aryl halides to access a broader range of anisoles and methoxypyridines and their trideuteriomethoxy derivatives, by using a sterically demanding BippyPhos-based phosphine ligand and t BuXPhos ligand, respectively. In addition, copper-catalyzed coupling of methanol with aryl iodides also serves as a convenient method to prepare anisoles . Despite these advances, the substrate scope is generally limited to aryl halides and halopyridines.…”

The Influence of Copper on Halogenation/Dehalogenation Reactions of Aromatic Compounds and Its Role in the Destruction of Polyhalogenated Aromatic Contaminants

“…Although relatively harsh conditions are used (135 • C), this procedure has genuine economic advantages in that very inexpensive materials are used (Scheme 29) [109]. The other published methods enable Cu-catalyzed coupling or aryl chlorides with phenols applied CuI nanoparticles [110], CuI/sparteine L13 [111], nano Cu2O [112] were achieved for diaryl ether synthesis starting from chlorobenzene.…”

“…On the other hand, in the area of treatment methods applicable for chemical destruction of toxic Ar-Cl derivatives are phenols as reactants much more expensive compared with sodium or potassium hydroxide, carbonate or phosphate applied in hydroxylation reactions. The other published methods enable Cu-catalyzed coupling or aryl chlorides with phenols applied CuI nanoparticles [110], CuI/sparteine L13 [111], nano Cu2O [112] were achieved for diaryl ether synthesis starting from chlorobenzene.…”

“…Although the intramolecular C-O coupling of aryl chloride with aromatic OH group catalyzed by copper(I) salts is much easier and is applicable for the preparation of diben- The other published methods enable Cu-catalyzed coupling or aryl chlorides with phenols applied CuI nanoparticles [110], CuI/sparteine L13 [111], nano Cu 2 O [112] were achieved for diaryl ether synthesis starting from chlorobenzene.…”