Negishi Coupling.doc

Negishi CouplingThe Negishi Coupling, published in 1977, was the first reaction that allowed the preparation of unsymmetrical biaryls in good yields. The versatile nickel- or palladium-catalyzed coupling of organozinc compounds with various halides (aryl, vinyl, benzyl, or allyl) has broad scope, and is not restricted to the formation of biaryls.Mechanism of the Negishi CouplingRecent LiteratureAn Extremely Active Catalyst for the Negishi Cross-Coupling ReactionJ. E. Milne, S. L. Buchwald, J. Am. Chem. Soc., 2004, 126, 13028-13032.One-Pot Negishi Cross-Coupling Reactions of In Situ Generated Zinc Reagents with Aryl Chlorides, Bromides, and TriflatesS. Sase, M. Jaric, A. Metzger, V. Malakhov, P. Knochel, J. Org. Chem., 2008, 73, 7380-7382.Efficient Negishi Coupling Reactions of Aryl Chlorides Catalyzed by Binuclear and Mononuclear Nickel-N-Heterocyclic Carbene ComplexesZ. Xi, Y. Zhou, W. Chen, J. Org. Chem., 2008, 73, 8497-8501.The First Negishi Cross-Coupling Reaction of Two Alkyl Centers Utilizing a Pd-N-Heterocyclic Carbene (NHC) CatalystN. Hadei, E. A. B. Kantchev, C. J. OBrien, M. G. Organ, Org. Lett., 2005, 7, 3805-3807.Negishi Coupling of Secondary Alkylzinc Halides with Aryl Bromides and ChloridesC. Han, S. L. Buchwald, J. Am. Chem. Soc., 2009, 131, 7532-7533.Effective Pd-Nanoparticle (PdNP)-Catalyzed Negishi Coupling Involving Alkylzinc Reagents at Room TemperatureJ. Liu, Y. Deng, H. Wang, H. Zhang, G. Yu, B. Wu, H. Zhang, Q. Li, T. B. Marder, Z. Yang, A. Lei, Org. Lett., 2008, 10, 2661-2664.Nickel-Catalyzed Asymmetric Negishi Cross-Couplings of Secondary Allylic Chlorides with AlkylzincsS. Son, G. C. Fu, J. Am. Chem. Soc., 2008, 130, 2756-2757.Efficient Cross-Coupling of Aryl Chlorides with Arylzinc Reagents Catalyzed by Amido Pincer Complexes of NickelL. Wang, Z.-X. Wang, Org. Lett., 2007, 9, 4335-4338.Highly Efficient, General Procedure for the Preparation of Alkylzinc Reagents from Unactivated Alkyl Bromides and ChloridesS. Huo, Org. Lett., 2003, 5, 423-425.Zn-Mediated, Pd-Catalyzed Cross-Couplings in Water at Room Temperature Without Prior Formation of Organozinc ReagentsA. Krasovskiy, C. Duplais, B. H. Lipshutz, J. Am. Chem. Soc., 2009, 131, 15592-15593.Palladium-Catalyzed Negishi Cross-Coupling Reactions of Unactivated Alkyl Iodides, Bromides, Chlorides, and TosylatesJ. Zhou, G. C. Fu, J. Am. Chem. Soc., 2003, 125, 12527-12530.Superior Effect of a -Acceptor Ligand (PhosphineElectron-Deficient Olefin Ligand) in the Negishi Coupling Involving Alkylzinc ReagentsX. Luo, H. Zhang, H. Duan, Q. Liu, L. Zhu, T. Zhang, A. Lei, Org. Lett., 2007, 9, 4571-4574.A nonionic amphiphile enables a simple approach to Pd-catalyzed stereoselective sp3-sp2 cross-couplings between alkyl and alkenyl bromides in the presence of zinc powder in water to give coupled products in good yields without prior formation of the organozinc reagents. The reaction is conducted at room temperature and tolerates various functional groups.A. Krasovskiy, C. Duplais, B. H. Lipshutz, Org. Lett., 2010, 12, 4742-4744.Iron-Catalyzed Negishi Coupling Toward an Effective Olefin SynthesisT. Niu, W. Zhang, D. Huang, C. Xu, H. Wang, Y. Hu, Org. Lett., 2009, 11, 4474-4477.Highly Regio- and Stereoselective Synthesis of (Z)-Trisubstituted Alkenes via Propyne Bromoboration and Tandem Pd-Catalyzed Cross-CouplingC. Wang, T. Tobrman, Z. Xu, E.-i. Negishi, Org. Lett., 2009, 11, 4092-4095.Highly Regioselective Synthesis of Trisubstituted Allenes via Lithiation of 1-Aryl-3-alkylpropadiene, Subsequent Transmetalation, and Pd-Catalyzed Negishi Coupling ReactionJ. Zhao, Y. Liu, S. Ma, Org. Lett., 2008, 10, 1521-1523.One-Pot Formation and Derivatization of Di- and Triynes Based on the Fritsch-Buttenberg-Wiechell RearrangementT. Luu, Y. Morisaki, N. Cunningham, R. R. Tykwinski, J. Org. Chem., 2007, 72, 9622-9629.Catalytic Enantioselective Negishi Reactions of Racemic Secondary Benzylic HalidesF. O. Arp, G. C. Fu, J. Am. Chem. Soc., 2005, 127, 10482-10483.Synthesis of the Precursor of Anti-Inflammatory Agents by Cross-Coupling Using Electrogenerated Highly Reactive ZincA. A. Jalil, N. Kurono, M. Tokuda, Synthesis, 2002, 2681-2686.General, Robust, and Stereocomplementary Preparation of -Ketoester Enol Tosylates as Cross-Coupling Partners Utilizing TsCl-N-Methylimidazole AgentsH. Nakatsuji, K. Ueno, T. Misaki, Y. Tanabe, Org. Lett., 2008, 10, 2131-2134.High Temperature Metalation of Functionalized Aromatics and Heteroaromatics using (tmp)2Zn2MgCl22LiCl and Microwave IrradiationS. Wunderlich, P. Knochel, Org. Lett., 2008, 10, 4705-4707.The use of Pd2(dba)3 and X-Phos as a ligand enables a mild Negishi cross-coupling of 2-heterocyclic organozinc reagents and aryl chlorides providing 2-aryl-substituted pyridines and thiophenes in high yields. An efficient method to generate the organozinc reagents at room temperature is also demon