Palladium-Catalyzed Couplings Literature Examples
Explore examples of palladium-catalyzed couplings including Heck and Sonogashira couplings for alkenes and alkynes, as well as Negishi, Stille, Suzuki-Miyaura, and Hiyama couplings using various elements. Learn about specific reaction details and applications in organic synthesis.
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Palladium-catalyzed couplings: Literature examples Heck and Sonogashira couplings (alkenes & alkynes) Negishi, Stille, Suzuki-Miyaura, Hiyama (Zn, Sn, B, Si) Martin A. Walker, SUNY Potsdam CC-BY-SA 3.0 license
alkene Simple Heck coupling Heck, R. F. Org. React. 1982, 27, 345.
alkene An intramolecular Heck coupling Heck coupling to a trisubstituted alkene is difficult, hence a more active trifluoroacetate catalyst is used. Note also how the double bond migrates ; this quite often occurs. Hong, C. Y.; Kado, N.; Overman, L. E. J. Am. Chem. Soc. 1993, 115, 11028-11029.
alkyne The Sonogashira coupling Use of the Sonogashira coupling to couple an alkyne with a vinyl iodide. The product (after removal of the TMS group) is (+)-obtusenyne, a metabolite of Laurencia red algae. Crimmins MT, Powell MT. " Enantioselective Total Synthesis of (+)-Obtusenyne", Journal of the American Chemical Society, 2003, 125 (25), 7592 7595. doi:10.1021/ja029956v
organozinc Negishi coupling dppe is a bidentate phosphine ligand Herbert, John M. Tetrahedron Lett. 2004, 45(4), 817 819.
organotin Stille coupling: Preparation of an aryl triflate, followed by a Stille coupling. Furstner A, Seidel G, Kindler N. "Macrocydes by Ring-Closing-Metathesis, XI 1: Syntheses of (R)-(+)-Lasiodiplodin, Zeranoi and Truncated Salicylihalamides", Tetrahedron1999, 55, 8215-8230. doi:10.1016/S0040-4020(99)00302-6
organoboron The Suzuki-Miyaura reaction The arylboronic acids & esters are often prepared from aryllithiums. Denton TT, Zhang X, Cashman JR. "5-Substituted, 6-Substituted, and Unsubstituted 3-Heteroaromatic Pyridine Analogues of Nicotine as Selective Inhibitors of Cytochrome P-450 2A6", Journal of Medicinal Chemistry, 2005, 48 (1), 224 239. doi:10.1021/jm049696n
organoboron Suzuki-Miyaura coupling in synthesis A typical use of the Suzuki-Miyaura coupling in synthesis is shown in Mandal's 2002 synthesis of (-)-ebelactone A. Note that here an alkylborane is used, easily prepared by hydroboration. dppf is a bidentate phosphine ligand. Mandal, AK. "Stereocontrolled Total Synthesis of (-)-Ebelactone A", Organic Letters, 2002, 4, 2043-2045. doi:10.1021/ol020058d
organoboron Molander variation of the Suzuki-Miyaura coupling This uses an alkyltrifluoroborate salt. Molander GA, Petrillo DE. "Suzuki-Miyaura Cross-Coupling of Potassium Trifluoroboratohomoenolates", Organic Letters, 2008, 10, 1795-1798. doi:10.1021/ol800357c
organosilane Hiyama coupling Pierrat P, Gros P, Fort Y. "Hiyama Cross-Coupling of Chloro-, Fluoro-, and Methoxypyridyltrimethylsilanes: Room-Temperature Novel Access to Functional Bi(het)aryl", Organic Letters, 2005, 7(4), 697-700. doi:10.1021/ol047482u
