Copper-catalyzed arylations amines alcohols

Copper-Catalyzed Arylations of Amines and Alcohols with Boron-Based Arylating Reagents... 

Although thiols are generally stronger nucleophiles than alcohols and amines, the sensitivity of sulfides towards oxidation as well as the formation of disulfide made the cross-coupling between aryl halides and thiols difficult. From all previously reported results, it was foimd that only aryl iodides were suitable for this copper-catalyzed coupling process. 

Mechanism of Copper-Catalyzed Coupling of Aryl Halides with Amines, Alcohols, and Thiols... 

Reaction of Alkyl Amines Copper-catalyzed cross-coupling of aliphatic amines with aryl halides has made considerable progress. Several methods have used Ctil with p-amino alcohols L58 [42], amino acids L59, L60 [43], Al,Al-diethyl saUcylaldehyde L61 [44], or p-diketones L62-L65 [45] (Fig. 20.3). Among these, the protocol using p-diketones exhibited the superior results catalyzing the reaction even at room temperature (Scheme 20.19). 

After the first works on the copper-catalyzed aiylation of alkyl amines in the presence of ethylene glycol (2 equiv.) L15 [134] or diethylsalicylamide (5-20 mol%) L16 [135] as ligands, Buchwald reported in 2006 a room-temperature procedure for this type of reaction (Scheme 4). The condensation of primary or secondary alkyl amines [136, 137], and amino alcohols (selective N- versus O-arylation) with aryl iodides was performed at 25°C, thanks to the help of cheap 1,3-diket(Mie ligands L17 associated with Cul (5%). Harsher cmiditions (90°C) had to be applied from aryl bromides (Scheme 4). 

Arylation of amines or alcohols catalyzed with copper are well documented (Fig. 3). 

ARYLATION OF AMINES AND ALCOHOLS CATALYZED BY NICKEL, COPPER OR PALLADIUM COMPLEXES... 

Scheme 4 Copper iodide /L17-catalyzed reactions of alkyl amines or and amino alcohols with aryl halides...

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