Buchwald-Hartwig.doc

Buchwald-Hartwig Cross Coupling ReactionPalladium-catalyzed synthesis of aryl amines. Starting materials are aryl halides or pseudohalides (for example triflates) and primary or secondary amines.The synthesis of aryl ethers and especially diaryl ethers has recently received much attention as an alternative to the Ullmann Ether Synthesis.Newer catalysts and methods offer a broad spectrum of interesting conversions.Mechanism of the Buchwald-Hartwig CouplingRecent Literature(CyPF-tBu)PdCl2: An Air-Stable, One-Component, Highly Efficient Catalyst for Amination of Heteroaryl and Aryl HalidesQ. Sheng, J. F. Hartwig, Org. Lett., 2008, 10, 4109-4112.A Multiligand Based Pd Catalyst for C-N Cross-Coupling ReactionsB. P. Fors, S. L. Buchwald, J. Am. Chem. Soc., 2010, 132, 15914-15917.Palladium-Catalyzed Coupling of Ammonia with Aryl Chlorides, Bromides, Iodides, and Sulfonates: A General Method for the Preparation of Primary ArylaminesG. D. Vo, J. F. Hartwig, J. Am. Chem. Soc., 2009, 131, 11049-11061.(IPr)Pd(acac)Cl: An Easily Synthesized, Efficient, and Versatile Precatalyst for C-N and C-C Bond FormationN. Marion, E. C. Ecarnot, O. Navarro, D. Amoroso, A. Bell, S. P. Nolan, J. Org. Chem., 2006, 71, 3816-3821.Synthesis of Bulky and Electron-Rich MOP-type Ligands and Their Applications in Palladium-Catalyzed C-N Bond FormationX. Xie, T. Y. Zhang, Z. Zhang, J. Org. Chem., 2006, 71, 6522-6529.Triazole-Based Monophosphine Ligands for Palladium-Catalyzed Cross-Coupling Reactions of Aryl ChloridesQ. Dai, W. Gao, D. Liu, L. M. Kapes, X. Zhang, J. Org. Chem., 2006, 71, 3928-3934.Bulky Alkylphosphines with Neopentyl Substituents as Ligands in the Amination of Aryl Bromides and ChloridesL. L. Hill, L. R. Moore, R. Huang, R. Craciun, A. J. Vincent, D. A. Dixon, J. Chou, C. J. Woltermann, K. H. Shaughnessy, J. Org. Chem., 2006, 71, 4951-4955.Water-Mediated Catalyst Preactivation: An Efficient Protocol for C-N Cross-Coupling ReactionsB. P. Fors, P. Krattiger, E. Strieter, S. L. Buchwald, Org. Lett., 2008, 10, 3505-3508.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 ChloridesB. P. Fors, D. A. Watson, M. R. Biscoe, S. L. Buchwald, J. Am. Chem. Soc., 2008, 130, 13552-13554.Palladium-Catalyzed Monoarylation of Aryl Amine with Aryl TosylatesX. Xie, G. Ni, F. Ma, L. Ding, S. Xu, Z. Zhang, Synlett, 2011, 955-958.Cross-Coupling and Dehalogenation Reactions Catalyzed by (N-Heterocyclic carbene)Pd(allyl)Cl ComplexesO. Navarro, H. Kaur, P. Mahjoor, S. P. Nolan, J. Org. Chem., 2004, 69, 3173-3180.Expedited Palladium-Catalyzed Amination of Aryl Nonaflates through the Use of Microwave-Irradiation and Soluble Organic Amine BasesR. E. Tundel, K. W. Anderson, S. L. Buchwald, J. Org. Chem., 2006, 71, 430-433.Palladium- and Nickel-Catalyzed Aminations of Aryl Imidazolylsulfonates and SulfamatesL. Ackermann, R. Sandmann, W. Song, Org. Lett., 2011, 13, 1784-1786.An Air and Thermally Stable One-Component Catalyst for the Amination of Aryl ChloridesD. Zim, S. L. Buchwald, Org. Lett., 2003, 5, 2413-2415.(t-Bu)2PNP(i-BuNCH2CH2)3N: New Efficient Ligand for Palladium-Catalyzed C-N Couplings of Aryl and Heteroaryl Bromides and Chlorides and for Vinyl Bromides at Room TemperatureCh. V. Reddy, J. V. Kingston, J. G. Verkade, J. Org. Chem., 2008, 73, 3047-3062.Use of Polymer-Supported Dialkylphosphinobiphenyl Ligands for Palladium-Catalyzed Amination and Suzuki-ReaktionsC. A. Parrish, S. L. Buchwald, J. Org. Chem., 2001, 66, 3820-3827.(t-Bu)2PNP(i-BuNCH2CH2)3N: New Efficient Ligand for Palladium-Catalyzed C-N Couplings of Aryl and Heteroaryl Bromides and Chlorides and for Vinyl Bromides at Room TemperatureCh. V. Reddy, J. V. Kingston, J. G. Verkade, J. Org. Chem., 2008, 73, 3047-3062.A Pd(0)-catalyzed C-N bond-forming reaction enables the synthesis of brominated indoles in the presence of PtBu3 as phosphine ligand. The bulky ligand serves to prevent inhibition of the catalyst by facilitating reversible oxidative addition into the product C-Br bond.S. G. Newman, M. Lautens, J. Am. Chem. Soc., 2010, 132, 11416-11417.A new reactivity pattern for vinyl bromides: cine-substitution via palladium catalysed C-N coupling/Michael addition reactionsM. C. Willis, J. Chauhan, W. G. Whittinham, Org. Biomol. Chem., 2005,