Hartwig-Buchwald C-N Bond Coupling

The palladium-catalyzed coupling reaction of aryl halides with the nitrogen atom from amines is generally known as the Hartwig-Buchwald reaction. The direct palladium-catalyzed C-N bond formation was first reported by Buchwald1 and Hartwig2 for the preparation of arylamines.

Palladium-Catalyzed Aromatic Aminations with in situ Generated Aminostannanes.
Guram, A. S.; Buchwald, S. L. J. Am. Chem. Soc. 1994, 116, 7901.

Palladium-catalyzed formation of carbon-nitrogen bonds. Reaction intermediates and catalyst improvements in the hetero cross-coupling of aryl halides and tin amides.
Paul, F.; Patt, J.; Hartwig, J. F. J. Am. Chem. Soc. 1994, 116, 5969.

 

Mechanism:

 

 

Recent publications:

Palladium-Catalyzed Method for the Synthesis of Carbazoles via Tandem C−H Functionalization and C−N Bond Formation.
W. C. Peter Tsang, Rachel H. Munday, Gordon Brasche, Nan Zheng and Stephen L. Buchwald*
J. Org. Chem.
, 2008, 73 (19), pp 7603–7610.

A Highly Active Catalyst for Pd-Catalyzed Amination Reactions: Cross-Coupling Reactions Using Aryl Mesylates and the Highly Selective Monoarylation of Primary Amines Using Aryl Chlorides.
Brett P. Fors, Donald A. Watson, Mark R. Biscoe and Stephen L. Buchwald*
J. Am. Chem. Soc., 2008, 130 (41), pp 13552–13554.

Pd-Catalyzed Amidations of Aryl Chlorides Using Monodentate Biaryl Phosphine Ligands:  A Kinetic, Computational, and Synthetic Investigation.
Takashi Ikawa, Timothy E. Barder, Mark R. Biscoe, and Stephen L. Buchwald*
J. Am. Chem. Soc., 2007, 129 (43), pp 13001–13007.

Simple, Efficient Catalyst System for the Palladium-Catalyzed Amination of Aryl Chlorides, Bromides, and Triflates.
John P. Wolfe, Hiroshi Tomori, Joseph P. Sadighi, Jingjun Yin, and Stephen L. Buchwald*
J. Org. Chem., 2000, 65 (4), pp 1158–1174.