Generic placeholder image

Current Organic Synthesis


ISSN (Print): 1570-1794
ISSN (Online): 1875-6271

Review Article

Application of Palladium-Catalyzed Cross-Coupling Reactions in Organic Synthesis

Author(s): Shalu Sain, Sonika Jain, Manish Srivastava, Rajendra Vishwakarma and Jaya Dwivedi*

Volume 16, Issue 8, 2019

Page: [1105 - 1142] Pages: 38

DOI: 10.2174/1570179416666191104093533

Price: $65


Palladium-catalyzed cross-coupling reactions have gained a continuously growing interest of synthetic organic chemists. The present review gives a brief account of applications of the palladium-catalyzed cross-coupling reactions in comprehensive synthesis, viz., the Heck, Stille, Suzuki–Miyaura, Negishi, Sonogashira, Buchwald–Hartwig, Ullmann and the Oxidative, decarboxylative cross-coupling reactions, with particular emphasis on the synthesis of heterocyclic compounds.

Keywords: Palladium catalyst, cross-coupling, Heck reaction, Suzuki-Miyaura, Stille, Sonogashira Coupling, Buchwald–Hartwig reaction, Ullmann reaction.

Graphical Abstract
Vlaar, T.; Ruijter, E.; Maes, B.U.W.; Orru, R.V.A. Palladium-catalyzed migratory insertion of isocyanides: an emerging platform in cross-coupling chemistry. Angew. Chem. Int. Ed. Engl., 2013, 52(28), 7084-7097.
[] [PMID: 23754476]
Herve, G.; Sartori, G.; Enderlin, G.; Mackenzie, G.; Len, C. Palladium-catalyzed Suzuki reaction in aqueous solvents applied to unprotected nucleosides and nucleotides. RSC Advances, 2014, 4, 18558-18594.
Hassine, A.; Bouhrara, M.; Sebti, S.; Solhy, A.; Luart, D.; Len, C.; Fihri, A. Natural phosphate-supported palladium: A highly efficient and recyclable catalyst for the Suzuki-Miyaura coupling under microwave irradiation. Curr. Org. Chem., 2014, 18(24), 3141-3148.
Opanasenko, M.; Stepnicka, P.; Cejka, J. Heterogeneous Pd catalysts supported on silicamatrices. RSC Advances, 2014, 4, 65137-65162.
Godoy, F.; Segarra, C.; Poyatos, M.; Peris, E. Palladium catalysts with sulfonate-functionalized-NHC ligands for Suzuki-Miyaura cross-coupling reactions in water. Organometallis, 2011, 30, 684-688.
Gildner, P.G.; Colacot, T.J. Reactions of the 21st century: Two decades of innovative catalyst design for palladium-catalyzed cross couplings. J. Am. Chem. Soc., 2015, 34, 5497-5508.
Xu, T.; Sha, F.; Alper, H. Highly Ligand-controlled regioselective Pd-catalyzed aminocarbonylation of styrenes with aminophenols. J. Am. Chem. Soc., 2016, 138(20), 6629-6635.
[] [PMID: 27159663]
Li, L.; Zhao, S.; Joshi-Pangu, A.; Mohamed, D.; Biscoe, M.R. Stereospecific Pd-catalyzed cross-coupling reactions of secondary alkylboron nucleophiles and aryl chlorides. J. Am. Chem. Soc., 2014, 136, 14027-14030.
Thomas, C. New Trends in Cross-Coupling: Theory and Applications. Johnson Matthey Technol. Rev., 2016, 60(2), 99-105.
(a) Alonso-Maranon, L.; Sarandeses, L.A.; Martinez, M.M.; Sestelo, J.P. Sequential In-catalyzed intra molecular hydroarylation and Pd-catalyzed cross-coupling reactions using bromopropargyl aryl ethers and amines. Org. Chem. Front., 2017, 4, 500-505.
(b) Alonso-Marañón, L.; Martínez, M.M.; Sarandeses, L.A.; Gómez-Bengoa, E.; Pérez Sestelo, J. Indium(III)-catalyzed synthesis of benzo[b]furans by intramolecular hydroalkoxylation of ortho-alkynylphenols: Scope and mechanistic insights. J. Org. Chem., 2018, 83(15), 7970-7980.
[] [PMID: 29890829]
(c) Kim, D.; Hong, S. Palladium(II)-catalyzed direct intermolecular alkenylation of chromones. Org. Lett., 2011, 13(16), 4466-4469.
[] [PMID: 21797199]
(d) Kumar, S.; Saunthwal, R.K.; Mujahid, M.; Aggarwal, T.; Verma, A.K. Palladium-Catalyzed Intramolecular Fujiwara-Hydroarylation: Synthesis of Benzo[a]phenazines Derivatives. J. Org. Chem., 2016, 81(20), 9912-9923.
[] [PMID: 27704818]
Yao, T.; Liu, T.; Zhang, C. Palladium-catalyzed domino Heck/intermolecular cross-coupling: Efficient synthesis of 4-alkylated isoquinoline derivatives. Chem. Commun. (Camb.), 2017, 53(15), 2386-2389.
[] [PMID: 28174767]
Friis, S.D.; Pirnot, M.T.; Dupuis, L.N.; Buchwald, S.L. A dual palladium and copper hydride catalyzed approach for alkyl-aryl cross-coupling of aryl halides and olefins. Angew. Chem. Int. Ed. Engl., 2017, 56(25), 7242-7246.
[] [PMID: 28510287]
Markovic, T.; Rocke, B.N.; Blakemore, D.C.; Mascitti, V.; Willis, M.C. Pyridine sulfinates as general nucleophilic coupling partners in palladium-catalyzed cross-coupling reactions with aryl halides. Chem. Sci. (Camb.), 2017, 8(6), 4437-4442.
[] [PMID: 28936330]
Thiery, E.; You, V.; Mora, A.S.; Mohamed, A. Synthesis of 5-substituted 1,2,3-triazolyl-4-phosphonate through cross-coupling reactions of 5-iodo-1,2,3-triazolyl-4-phosphonate. Eur. J. Org. Chem., 2016, 2016, 529-534.
Cheval, N.P.; Dikova, A.; Blanc, A.; Weibel, J.M.; Pale, P. Vinyl nosylates: An ideal partner for palladium-catalyzed cross-coupling reactions. Chemistry, 2013, 19(27), 8765-8768.
[] [PMID: 23695947]
Pareek, M.; Fallon, T.; Oestreich, M. Platinum(0)-catalyzed indolyne insertion into bis(pinacolato)diboron followed by site-selective Suzuki-Miyaura cross-coupling. Org. Lett., 2015, 17(9), 2082-2085.
[] [PMID: 25880022]
Igarashi, T.; Tobisu, M.; Chatani, N. Catalytic double carbon–boron bond formation for the synthesis of cyclic diaryl boronic acids as versatile building blocks for p-extended heteroarenes. Chem. Int. Ed., 2017, 56, 2069-2073.
(a) Takeda, Y.; Ikeda, Y.; Akinobu, K.; Tanaka, S.; Minakata, S. d/NHC-catalyzed enantiospecific and regioselective Suzuki−Miyaura arylation of 2-arylaziridines: synthesis of enantioenriched 2-arylphenethylamine derivatives. J. Am. Chem. Soc., 2014, 136, 8544-8547. http://10.1021/ja5039616
b)Wong, P.Y.; Chow, W.K.; Chung, K.H.; So, C.M.; Lau, C.P.; Kwong, F.Y. A versatile palladium catalyst system for Suzuki-Miyaura coupling of alkenyl tosylates and mesylates. Chem. Commun. (Camb.), 2011, 47(29), 8328-8330.
[] [PMID: 21681318]
Wang, T.; Yang, S.; Xu, S.; Han, C.; Guob, G.; Zhao, J. Palladium catalyzed Suzuki cross-coupling of benzyl trimethyl ammonium salts via C–N bond cleavage. RSC Advances, 2017, 7, 15805-15808.
Lei, P.; Meng, G.; Szostak, M. General method for the Suzuki−Miyaura cross-coupling of amides using commercially available, air- and moisture-stable palladium/NHC (NHC = N-heterocyclic carbene). complexes. ACS Catal., 2017, 7, 1960-1965.
Colleville, A.P.; Richard, A.J.H.; Tomkinson, N.C.O. Aryldiazonium tetra-fluoroborate salts as green and efficient coupling partners for the Suzuki−Miyaura reaction: From optimisation to mole scale. Org. Process Res. Dev., 2014, 18, 1128-1136.
(a) Teh, W.P.; Michael, F.E. Palladium-catalyzed cross-coupling of N-sulfonylaziridines and alkenylboronic acids: Stereospecific synthesis of homoallylic amines with di- and trisubstituted alkenes. Org. Lett., 2017, 19(7), 1738-1740.
[] [PMID: 28296408]
(b) Li, C.; Xing, J.; Zhao, J.; Huynh, P.; Zhang, W.; Jiang, P.; Zhang, Y.J. Pd-catalyzed regioselective and stereospecific Suzuki-Miyaura coupling of allylic carbonates with arylboronic acids. Org. Lett., 2012, 14(1), 390-393.
[] [PMID: 22185574]
(c) Chausset-Boissarie, L.; Ghozati, K.; LaBine, E.; Chen, J.L-Y.; Aggarwal, V.K.; Crudden, C.M. Enantiospecific, regioselective cross-coupling reactions of secondary allylic boronic esters. Chemistry, 2013, 19(52), 17698-17701.
[] [PMID: 24302640]
Shendage, S.S.; Singh, A.S.; Nagarkar, J.M. Facile approach to the electrochemical synthesis of palladium-reduced graphene oxide and its application for Suzuki coupling reaction. Tetrahedron Lett., 2014, 55(4), 857-860.
Shendage, S.S.; Patil, U.B.; Nagarkar, J.M. Electrochemical synthesis and characterization of palladium nanoparticles on nafion–graphene support and its application for Suzuki coupling reaction. Tetrahedron Lett., 2013, 54(26), 3457-3461.
(a) Balsane, K.E.; Shelkar, R.S.; Nagarkar, J.M. Electrochemical synthesis of Pd nano particles on pencil-graphite and application for Suzuki coupling reactions. Catal. Lett., 2015, 145(10), 1817-1824. http://10.1007/s10562-015-1571-y
(b) Scheuermann, G.M.; Rumi, L.; Steurer, P.; Bannwarth, W.; Mülhaupt, R. Palladium nanoparticles on graphite oxide and its functionalized graphene derivatives as highly active catalysts for the Suzuki-Miyaura coupling reaction. J. Am. Chem. Soc., 2009, 131(23), 8262-8270.
[] [PMID: 19469566]
(c) Qu, K.; Wu, L.; Jinsong, R.; Xiaogang, Q. Natural DNA-modified graphene/Pd nanoparticles as highly active catalyst for formic acid electro-oxidation and for the Suzuki Reaction. ACS Appl. Mater., 2012, 4, 5001-5009.
Pereira, R.; Cvengros, J. Troger’s base derived phosphanes for Suzuki–Miyaura and Buchwald–Hartwig cross-coupling reactions. Eur. J. Org. Chem., 2013, 2013, 4233-4237.
(a) Quan, Z-J.; Jing, F-Q.; Da Zhang, Z.Y-X.; Wang, X-C. Palladium(II) catalyzed Suzuki/Sonogashira cross-coupling reactions of sulfonates: An efficient approach to C2-functionalized pyrimidines and pyridines. Eur. J. Org. Chem., 2013, 7175-7183.
(b) Li, Y.; Tang, J.; Gu, J.; Wang, Q.; Sun, P.; Zhang, D. Chiral 1,2-cyclohexane-bridged bis-NHC Palladium catalysts for asymmetric Suzuki-Miyaura coupling: synthesis, characterization, and steric effects on enantiocontrol. Organometallics, 2014, 33, 876-884.
(c) Miyaura, N.; Suzuki, A. Palladium-catalyzed cross-coupling reactions of organoboron compounds. Chem. Rev., 1995, 95(7), 2457-2483.
(a) Delaye, P-O.; Pénichon, M.; Allouchi, H.; Enguehard-Gueiffier, C.; Gueiffier, A. Regiocontrolled functionalization of 2,3-dihalogenoimidazo[1,2-a]pyridines by Suzuki-Miyaura and Sonogashira cross-coupling reactions. Org. Biomol. Chem., 2017, 15(19), 4199-4204.
[] [PMID: 28443935]
(b) Gholap, A.R.; Venkatesan, K.; Pasricha, R.; Daniel, T.; Lahoti, R.J.; Srinivasan, K.V. Copper- and ligand-free Sonogashira reaction catalyzed by Pd(0) nanoparticles at ambient conditions under ultrasound irradiation. J. Org. Chem., 2005, 70(12), 4869-4872.
[] [PMID: 15932333]
(c) Wu, Y.; Xing, Y.; Wang, J.; Sun, Q.; Kong, W.; Suzenet, F. Palladium-catalyzed desulfurative Sonogashira cross-coupling reaction of 3-cyano assisted thioamide-type quinolone derivatives with alkynes. RSC Advances, 2015, 5, 48558-48562.
Kumar, S.; Saleem, F.; Mishrab, M.K.; Singh, A.K. Oxine based unsymmetrical (O_, N, S/Se) pincer ligands and their palladium (II) complexes: synthesis, structural aspects and applications as a catalyst in amine and copper-free Sonogashira coupling. New J. Chem., 2017, 41, 2745-2755.
Yu, B.; Sun, H.; Xie, Z.; Zhang, G.; Xu, L-W.; Zhang, W.; Gao, Z. Privilege ynone synthesis via palladium-catalyzed alkynylation of “Super-Active Esters”. Org. Lett., 2015, 17(13), 3298-3301.
[] [PMID: 26065590]
Fukuyama, T.; Shinmen, M.; Nishitani, S.; Sato, M.; Ryu, I. A copper-free Sonogashira coupling reaction in ionic liquids and its application to a microflow system for efficient catalyst recycling. Org. Lett., 2002, 4(10), 1691-1694.
[] [PMID: 12000275]
(a) Lu, G-p.; Caib, C.; Lipshutz, B.H. Stille couplings in water at room temperature. Green Chem., 2013, 15, 105-109.
(b) Stille, J.K.; Groh, B.L. Stereospecific cross-coupling of vinyl halides with vinyl tin reagents catalyzed by palladium. J. Am. Chem. Soc., 1987, 109(3), 813-817.
(c) Stille, J.K. Palladium catalyzed coupling of organotin reagents with organic electrophiles. Pure Appl. Chem., 1985, 57(12), 1771-1780.
(d) Rai, R.; Aubrecht, K.B.; Collum, D.B. Palladium-catalyzed stille couplings of aryl-, vinyl-, and alkyl tri-chlorstannanes in aqueous solution. Tetrahedron Lett., 1995, 36(18), 3111-3114.
(a) DeAngelis, A.; Wang, D.H.; Buchwald, S.L. Mild and rapid Pd-catalyzed cross-coupling with hydrazine in continuous flow: application to the synthesis of functionalized heterocycles. Angew. Chem. Int. Ed. Engl., 2013, 52(12), 3434-3437.
[] [PMID: 23404773]
(b) Ruiz-Castillo, P.; Buchwald, S.L. Applications of palladium-catalyzed C-N cross-coupling reactions. Chem. Rev., 2016, 116(19), 12564-12649.
[] [PMID: 27689804]
(a) Ayogu, J.I.; Enoo, O.; Okoro, U.C. Synthesis of 6-anilino derivatives of benzo[a]phenoxazin-5-one and related aza analogues via palladium-catalyzed Buchwald-Hartwig amination reaction. Int. J. Sci. Res. (Ahmedabad), 2017, 6(4), 2319-7064.
(b) Zhang, L.; Huang, X.; Zhen, S.; Zhao, J.; Li, H.; Yuan, B.; Yang, G. Pd-catalyzed double N-arylation of primary amines to synthesize phenoxazines and phenothiazines. Org. Biomol. Chem., 2017, 15(30), 6306-6309.
[] [PMID: 28715031]
(a) Wagner, P.; Bollenbach, M.; Doebelin, C.; Bihel, F.; Bourguignon, J-J.; Salome, C.; Schmitt, M. t-BuXPhos: A highly efficient ligand for Buchwald–Hartwig coupling in water. Green Chem., 2014, 16, 4170-4178.
(b) Rao, R.K.; Karthikeyan, I.; Sekar, G. Domino aziridine ring opening and Buchwald–Hartwig type coupling-cyclization by palladium catalyst. Tetrahedron, 2012, 68(44), 9090-9094.
Liu, Z.; Dong, N.; Xu, M.; Sun, Z.; Tao, T. Mild negishi cross-coupling reactions catalyzed by acenaphthoimidazolylidene palladium complexes at low catalyst loadings. J. Org. Chem., 2013, 78, 7436-7444.
Vasudev, R. Bhonde, Neill, B. T.; Buchwald, S.L. An improved system for the aqueous Lipshutz–Negishi cross-coupling of alkyl halides with aryl electrophiles. Angew. Chem. Int. Ed., 2016, 55, 1849-1853.
Yang, Y.; Oldenhuis, N.J.; Buchwald, S.L. Mild and general conditions for negishi cross-coupling enabled by the use of palladacycle precatalysts. Angew. Chem. Int. Ed. Engl., 2013, 52(2), 615-619.
[] [PMID: 23172689]
Yang, Y.; Niedermann, K.; Han, C.; Buchwald, S.L. Highly selective palladium-catalyzed cross-coupling of secondary alkylzinc reagents with heteroaryl halides. Org. Lett., 2014, 16, 4638-4641.
Campos, V.R.; Gomes, A.T.P.C.; Cunha, A.C.; Neves, M.D.; Ferreira, V.F.; Cavaleiro, J.A.S. Efficient access to β-vinylporphyrin derivatives via palladium cross coupling of β-bromoporphyrins with N-tosylhydrazones. Beilstein J. Org. Chem., 2017, 13, 195-202.
[] [PMID: 28228860]
Manley, P.; Acemoglu, M.; Marterer, W.; Pachinger, W. Large-scale negishi coupling as applied to the synthesis of PDE472, an inhibitor of phosphodiesterase type 4D. Org. Process Res. Dev., 2003, 7(3), 436-445.
Shimizu, N.; Kitamura, T.; Watanabe, K.; Yamaguchi, T. A simple and efficient synthesis of 2,- 3-, or 4-(2-nitrophenyl)pyridine derivatives via palladium catalyzed ullmann cross-coupling reaction. Tetrahedron Lett., 1993, 34, 3421-3424 (for earlier work that resulted in less efficient outcomes see: Thompson, W. J.; Gaudino. J. A general synthesis of 5-arylnicotinates. J. Org. Chem., 1984, 49, 5237-5243.
Ackerman, L.K.G.; Lovell, M.M.; Weix, D.J. Multimetallic catalysed cross-coupling of aryl bromides with aryl triflates. Nature, 2015, 524(7566), 454-457.
[] [PMID: 26280337]
Banwell, M.G.; Kelly, B.D.; Kokas, O.J.; Lupton, D.W. Synthesis of indoles via palladium[0]-mediated Ullmann cross-coupling of o-halonitroarenes with α-halo-enones or -enals. Org. Lett., 2003, 5(14), 2497-2500.
[] [PMID: 12841764]
Banwell, M.G.; Jones, M.T.; Reekie, T.A. The palladium-catalysed ullmann cross-coupling reaction. Chem. N. Z., 2011, 75, 122-127.
(a) Hackenberger, D.; Weber, P.; Blakemore, D.C.; Goossen, L.J.J. Synthesis of 3-substituted 2-arylpyridines via Cu/Pd-catalyzed decarboxylative cross-coupling of picolinic acids with (hetero)aryl halides. J. Org. Chem., 2017, 82(7), 3917-3925.
[] [PMID: 28300402]
(b) Goossen, L.J.; Zimmermann, B.; Knauber, T. Palladium/copper-catalyzed decarboxylative cross-coupling of aryl chlorides with potassium carboxylates. Angew. Chem. Int. Ed. Engl., 2008, 47(37), 7103-7106.
[] [PMID: 18683265]
(c) He, R-T.; Wang, J-F.; Wang, H-F.; Ren, Z-G.; Lang, J-P. Palladium dichloride adduct of N,N-bis-(diphenylphosphanylmethyl)-2-aminopyridine: synthesis, structure and catalytic performance in the decarboxylative cross-coupling of 4-picolinic acid with aryl bromide. Dalton Trans., 2014, 43(25), 9786-9794.
[] [PMID: 24848973]
Chen, T-H.; Reddy, D.M.; Lee, C.F.A. Palladium-catalyzed oxidative cross-coupling reaction between aryl pinacol boronates and H-phosphonates in ethanol. RSC Advances, 2017, 7, 30214-30220.
(a) Zhu, F.; Wang, Z.X. Palladium-catalyzed coupling of azoles or thiazoles with aryl thioethers via C-H/C-S activation. Org. Lett., 2015, 17(6), 1601-1604.
[] [PMID: 25719516]
(b) Chan, C.W.; Zhou, Z.; Chan, A.S.C.; Yu, W.Y. Pd-catalyzed ortho-C-H acylation/cross coupling of aryl ketone O-methyl oximes with aldehydes using tert-butyl hydroperoxide as oxidant. Org. Lett., 2010, 12(17), 3926-3929.
[] [PMID: 20704334]
Jie, X.; Shang, Y.; Hu, P.; Su, W. Palladium-catalyzed oxidative cross-coupling between heterocycles and terminal alkynes with low catalyst loading. Angew. Chem. Int. Ed. Engl., 2013, 52(13), 3630-3633.
[] [PMID: 23404782]
(a) Mantenuto, S.; Ciccolini, C.; Lucarini, S.; Piersanti, G.; Favi, G.; Mantellini, F. Palladium(II)-catalyzed intramolecular oxidative C-H/C-H cross-coupling reaction of C3,N-linked biheterocycles: Rapid access to polycyclic nitrogen heterocycles. Org. Lett., 2017, 19(3), 608-611.
[] [PMID: 28094964]
(b) Liu, C.; Zhang, H.; Shi, W.; Lei, A. Bond formations between two nucleophiles: transition metal catalyzed oxidative cross-coupling reactions. Chem. Rev., 2011, 111(3), 1780-1824.
[] [PMID: 21344855]
(c) Xi, P.; Yang, F.; Qin, S.; Zhao, D.; Lan, J.; Gao, G.; Hu, C.; You, J. Palladium(II)-catalyzed oxidative C-H/C-H cross-coupling of heteroarenes. J. Am. Chem. Soc., 2010, 132(6), 1822-1824.
[] [PMID: 20102197]
(a) Stuart, D.R.; Villemure, E.; Fagnou, K. Elements of regiocontrol in palladium-catalyzed oxidative arene cross-coupling. J. Am. Chem. Soc., 2007, 129(40), 12072-12073.
[] [PMID: 17880083]
(b) Das, D.; Bhutia, Z.T.; Chatterjee, A.; Banerjee, M. Mechanochemical Pd(II)-catalyzed direct and C-2-selective arylation of indoles. J. Org. Chem., 2019, 84(17), 10764-10774.
(a) Fu, L.; Mighion, J.D.; Voight, E.A.; Davies, H.M.L. Synthesis of 2,2,2,-trichloroethyl aryl- and vinyldiazoacetates by palladium-catalyzed cross-coupling. Chemistry, 2017, 23(14), 3272-3275.
[] [PMID: 28093820]
(b) Dobrounig, P.; Trobe, M.; Breinbauer, R. Sequential and iterative Pd-catalyzed cross-coupling reactions in organic synthesis. Monatsh. Chem., 2017, 148(1), 3-35.
[] [PMID: 28127089]
Shen, G.; Yang, B.; Huang, X.; Hou, Y.; Gao, H.; Cui, J.; Cui, C.; Zhang, T. Copper- and palladium-catalyzed cross-coupling reactions for the synthesis of N-fused benzo[4,5]imidazo[2,1-b]thiazole derivatives via substituted trans-1,2-diiodoalkenes, 1H-benzo[d]imidazole-2-thiols, and halobenzenes. J. Org. Chem., 2017, 82(7), 3798-3805.
[] [PMID: 28299941]
Luo, H.; Wu, G.; Xu, S.; Wang, K.; Wu, C.; Zhang, Y.; Wang, J. Palladium-catalyzed cross-coupling of aryl fluorides with N-tosylhydrazones via C-F bond activation. Chem. Commun. (Camb.), 2015, 51(68), 13321-13323.
[] [PMID: 26207857]

Rights & Permissions Print Export Cite as
© 2023 Bentham Science Publishers | Privacy Policy