Jwanro Hassan,Marc Se vignon,Christel Gozzi,Emmanuelle Schulz,and arc Lemaire*′,

Laboratoire de Catalyse et Synthe` se Organique, UMR 5622, Universite Claude ′Bernard Lyon 1, CPE, 43 Bd du 11 Novembre 1918, 69622 Villeurbanne Cedex, France, and Laboratoire de Catalyse Moleculaire, UPRESA,CNRS 8075, Institut de Chimie Mole ′culaire d’Orsay,Universite Paris-Sud, 91405 Orsay Cedex, France′

Aryl-Aryl Bond Formation

Chem. Rev. 2002, 102, 1359 1469

The first type is the Ullmann reaction.

The third type is clearly an oxidation of two C-H aromatic bonds to form a C-C bond.

The second type is closely related to the first but involves the formation of an aryl carbanion as the intermediate.

The fourth type and last one is the Pschorr reaction.

1. Aryl Aryl Bond Formation Using Copper as Reagent or Catalyst1.1. Reductive Coupling of Aromatic Halides (The Ullmann Reaction)A. Aromatic Coupling Using Stoichiometric Amount of Copper

a. Symmetrical Couplings.

b. Unsymmetrical Couplings.

B. Aromatic Coupling Using Catalytic Amounts of Copper

1.2. Coupling of Aromatics via Aryl CarbanionA. Use of Stoichiometric Amounts of Coppera. Symmetrical Couplings.

i. Coupling of Silicon Derivatives.

ii. Coupling of Tin Derivatives.

b. Unsymmetrical Couplings.

i. Coupling of Silicon Derivatives.

ii. Coupling of Lithium Derivatives.

B. Catalytic Amounts of Copper

a. Symmetrical Couplings.

i. Coupling of Silicon Derivatives.

ii. Coupling of Tin Derivatives.

b. Unsymmetrical Couplings. i. Coupling of Tin Derivatives. ii. Coupling of Boron Derivatives.

1.3. Oxidative Aromatic Coupling Using Copper Salts

A. Use of Stoichiometric Amount of Coppera. Symmetrical Couplings.

b. Unsymmetrical Couplings.

B. Use of Catalytic Amounts of Coppera. Symmetrical Couplings.

b. Unsymmetrical Couplings.

c. Oxidative Coupling with FeCl3.

4. Aromatic Coupling via Radicals (The Pschorr Reaction) Using Copper Salts

1.5. Synthesis of Oligomers and Polymers Using Copper as a Reagent

A. The Ullmann Reaction

B. Oxidative Coupling of an Activated Aryla. Using Copper as the Oxidative Reagent.

b. Using Iron as the Oxidative Reagent.

C. Chemical Polymerization Induced by Iron