美国化学家 RichardF.Heck 日本科学家根岸荣一和铃木章
① Heck Reaction
The palladium-catalyzed C-C coupling between aryl halides or vinyl halides and activated alkenes in the presence of a base is referred as the "Heck Reaction". Recent developments in the catalysts and reaction conditions have resulted in a much broader range of donors and acceptors being amenable to the Heck Reaction. One of the benefits of the Heck Reaction is its outstanding trans selectivity. 机理
An Efficient and General Method for the Heck and Buchwald-Hartwig Coupling Reactions of Aryl Chlorides D.-H. Lee, A. Taher, S. Hossain, M.-J. Jin, Org. Lett., 2011, 13, 5540-5543.
Palladium-Catalyzed Heck Reaction of Aryl Chlorides under Mild Conditions Promoted by
Organic Ionic Bases H.-J. Xu, Y.-Q. Zhao, X.-F. Zhou, J. Org. Chem., 2011, 76, 8036-8041.
Efficient Aqueous-Phase Heck Reaction Catalyzed by a Robust Hydrophilic Pyridine-Bridged Bisbenzimidazolylidene-Palladium Pincer Complex Z. Wang, X. Feng, W. Fang, T. Tu, Synlett, 2011, 951-954.
An efficient and simple protocol for phosphine-free Heck reactions in water in the presence of a Pd(L-proline)2 complex as the catalyst under controlled microwave irradiation conditions is versatile and provides excellent yields of products in short reaction times. The reaction system minimizes costs, operational hazards and environmental pollution. B. K. Allam, K. N. Singh, Synthesis, 2011, 1125-1131.
② Suzuki Coupling
The scheme above shows the first published Suzuki Coupling, which is the palladium-catalysed cross coupling between organoboronic acid and halides. Recent catalyst and methods developments have broadened the possible applications enormously, so that the scope of the reaction partners is not restricted to aryls, but includes alkyls, alkenyls and alkynyls. Potassium trifluoroborates and organoboranes or boronate esters may be used in place of boronic acids. Some pseudohalides (for example triflates) may also be used as coupling partners.
One difference between the Suzuki mechanism and that of the Stille Coupling is that the boronic acid must be activated, for example with base. This activation of the boron atom enhances the polarisation of the organic ligand, and facilitates transmetallation. If starting materials are substituted with base labile groups (for example esters), powdered KF effects this activation while leaving base labile groups unaffected.
In part due to the stability, ease of preparation and low toxicity of the boronic acid compounds, there is currently widespread interest in applications of the Suzuki Coupling, with new developments and refinements being reported constantly.
Stereoconvergent Amine-Directed Alkyl-Alkyl Suzuki Reactions of Unactivated Secondary Alkyl Chlorides Z. Lu, A. Wilsily, G. C. Fu, J. Am. Chem. Soc., 2011, 133, 8154-8157
Recyclable Catalysts for Suzuki-Miyaura Cross-Coupling Reactions at Ambient Temperature Based on a Simple Merrifield Resin Supported Phenanthroline-Palladium(II) Complex J. Yang, P. Li, L. Wang, Synthesis, 2011, 1295-1301
An Efficient and Recyclable Magnetic-Nanoparticle-Supported Palladium Catalyst for the Suzuki Coupling Reactions of Organoboronic Acids with Alkynyl Bromides X. Zhang, P. Li, Y. Ji, L. Zhang, L. Wang, Synthesis, 2011, 2975-2983.
Efficient Palladium-Catalyzed Cross-Coupling Reaction of Alkynyl Halides with Organoboronic Acids under Aerobic Conditions J.-S. Tang, M. Tian, W.-B. Sheng, C.-C. Guo, Synthesis, 2012, 541-546.
Ni(COD)2/PCy3 Catalyzed Cross-Coupling of Aryl and Heteroaryl Neopentylglycolboronates with Aryl and Heteroaryl Mesylates and Sulfamates in THF at Room Temperature P. Leowanawat, N. Zhang, A.-M. Remerita, B. M. Rosen, V. Percec, J. Org. Chem., 2011, 76, 9946-9955
The 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.
Highly Selective Reactions of Unbiased Alkenyl Halides and Alkylzinc Halides: Negishi-Plus Couplings A. Krasovskiy, B. H. Lipshutz, Org. Lett., 2011, 13, 3822-3825.
Ligand Effects on Negishi Couplings of Alkenyl Halides A. Krasovskiy, B. H. Lipshutz, Org. Lett., 2011, 13, 3818-3821.
A nonionic amphiphile enables a simple approach to Pd-catalyzed stereoselective sp -sp
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 Synthesis T. 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-Coupling C. 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 Reaction J. Zhao, Y. Liu, S. Ma, Org. Lett., 2008, 10, 1521-1523.