Rosenmund-von Braun Reaction
There are two different transformations referred as the Ullmann Reaction. The "classic" Ullmann Reaction is the synthesis of symmetric biaryls via copper-catalyzed coupling. The "Ullmann-type" Reactions include copper-catalyzed Nucleophilic Aromatic Substitution between various nucleophiles (e.g. substituted phenoxides) with aryl halides. The most common of these is the Ullmann Ether Synthesis.
Mechanism of the Ullmann Reaction
Biaryls are available through coupling of the aryl halide with an excess of copper at elevated temperatures (200 °C). The active species is a copper(I)-compound which undergoes oxidative addition with the second equivalent of halide, followed by reductive elimination and the formation of the aryl-aryl carbon bond.
The organocopper intermediate can be generated at a more moderate 70 °C using a novel thiophenecarboxylate reagent. The reaction otherwise follows the same reaction path as above.
Another possibility is the use of Cu(I) for the oxidative coupling of aryllithium compounds at low temperatures. This method can also be used to generate asymmetric biaryls, after addition of the appropriate halide.
Ullmann-type reactions proceed through a catalytic cycle, and in one mechanism the copper is postulated to undergo oxidation to Cu(III). As some Cu(III) salts have been prepared, the suggestion for the mechanism is intriguing (see also Chan-Lam Coupling):
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