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.
Mechanism of the Suzuki Coupling
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.
Boronic Acids: New Coupling Partners in Room-Temperature Suzuki Reactions of Alkyl Bromides. Crystallographic Characterization of an Oxidative-Addition Adduct Generated under Remarkably Mild Conditions
J. H. Kirchhoff, M. R. Netherton, I. D. Hill, G. C. Fu, J. Am. Chem. Soc., 2002, 124, 13662-13663.
Stereospecific Pd-Catalyzed Cross-Coupling Reactions of Secondary Alkylboron Nucleophiles and Aryl Chlorides
L. Li, S. Zhao, A. Joshi-Pangu, M. Diane, M. R. Biscoe, J. Am. Chem. Soc., 2014, 136, 14027-14030.
Rational Exploration of N-Heterocyclic Carbene (NHC) Palladacycle Diversity: A Highly Active and Versatile Precatalyst for Suzuki-Miyaura Coupling Reactions of Deactivated Aryl and Alkyl Substrates
G.-R. Peh, E. A. B. Kantchev, J.-C. Er, J. Y. Ying, Chem. Eur. J., 2010, 14, 4010-4017.
A Concise and Atom-Economical Suzuki-Miyaura Coupling Reaction Using Unactivated Trialkyl- and Triarylboranes with Aryl Halides
H. Li, Y.-L. Zhong, C.-y. Chen, A. E. Ferraro, D. Wang, Org. Lett., 2015, 17, 3616-3619.
An Indefinitely Air-Stable σ-NiII Precatalyst for Quantitative Cross-Coupling of Unreactive Aryl Halides and Mesylates with Aryl Neopentylglycolboronates
J. Malineni, R. L. Jezorek, N. Zhang, V. Percec, Synthesis, 2016, 48, 2795-2807.
Copper-Catalyzed Suzuki-Miyaura Coupling of Arylboronate Esters: Transmetalation with (PN)CuF and Identification of Intermediates
S. K. Gurung, S. Thapa, A. Kafle, D. A. Dickie, R. Giri, Org. Lett., 2014, 16, 1264-1267.
A Triarylphosphine Ligand Bearing Dodeca(ethylene glycol) Chains: Enhanced Efficiency in the Palladium-Catalyzed Suzuki-Miyaura Coupling Reaction
T. Fujihara, S. Yoshida, J. Terao, Y. Tsuji, Org. Lett., 2009, 11, 2121-2124.
A New Family of Tunable Indolylphosphine Ligands by One-Pot Assembly and Their Applications in Suzuki-Miyaura Coupling of Aryl Chlorides
C. M. So, C. C. Yeung, C. P. Lau, F. Y. Kwong, J. Org. Chem., 2008, 73, 7803-7806.
An Active, General, and Long-Lived Palladium Catalyst for Cross-Couplings of Deactivated (Hetero)aryl Chlorides and Bromides with Arylboronic Acids
T. Hoshi, T. Honma, A. Mori, M. Konishi, T. Sato, H. Hagiwara, T. Suzuki, J. Org. Chem., 2013, 78, 11513-11524.
Biphenylene-Substituted Ruthenocenylphosphine for Suzuki-Miyaura Coupling of Aryl Chlorides
T. Hoshi, T. Nakazawa, I. Saitoh, Y. Mori, T. Suzuki, J.-i. Sakai, H. Hagiwara, S. Akai, Org. Lett., 2008, 10, 2063-2066.
Scope of the Two-Step, One-Pot Palladium-Catalyzed Borylation/Suzuki Cross-Coupling Reaction Utilizing Bis-Boronic Acid
G. A. Molander, S. L. J. Trice, S. M. Kennedy, J. Org. Chem., 2012, 77, 8678-8688.
Facile Synthesis of Highly Stable Gold Nanoparticles and Their Unexpected Excellent Catalytic Activity for Suzuki-Miyaura Cross-Coupling Reaction in Water
J. Han, Y. Liu, R. Guo, J. Am. Chem. Soc., 2009, 131, 2060-2061.
Robust Acenaphthoimidazolylidene Palladium Complexes: Highly Efficient Catalysts for Suzuki-Miyaura Couplings with Sterically Hindered Substrates
T. Tu, Z. Sun, W. Fang, M. Xu, Y. Zhou, Org. Lett., 2012, 14, 4250-4253.
An N-Heterocyclic Carbene Ligand with Flexible Steric Bulk Allows Suzuki Cross-Coupling of Sterically Hindered Aryl Chlorides at Room Temperature
G. Altenhoff, R. Goddard, C. W. Lehmann, F. Glorius, Angew. Chem. Int. Ed., 2003, 42, 3690-3693.
Synthesis and Characterization of R2PN=P(iBuNCH2CH2)3N: A New Bulky Electron-Rich Phosphine for Efficient Pd-Assisted Suzuki-Miyaura Cross-Coupling Reactions
J. V. Kingston, J. G. Verkade, J. Org. Chem., 2007, 72, 2816-2822.
Modified (NHC)Pd(allyl)Cl (NHC = N-Heterocyclic Carbene) Complexes for Room-Temperature Suzuki-Miyaura and Buchwald-Hartwig Reactions
N. Marion, O. Navarro, J. Mei, E. D. Stevens, N. M. Scott, S. P. Nolan, J. Am. Chem. Soc., 2006, 128, 4101-4111.
Palladium catalyzed Suzuki-Miyaura coupling with aryl chlorides using a bulky phenanthryl N-heterocyclic carbene ligand
C. Song, Y. Ma, Q. Chai, C. Ma, W. Jiang, M. B. Andrus, Tetrahedron, 2005, 61, 7438-7446.
PVC-Supported Palladium Nanoparticles: An Efficient Catalyst for Suzuki Cross-Coupling Reactions at Room Temperature
M. Samarasimhareddy, G. Prabhu, T. M. Vishwanatha, V. V. Sureshbabu, Synthesis, 2013, 45, 1201-1206.
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.
PdEDTA Held in an Ionic Liquid Brush as a Highly Efficient and Reusable Catalyst for Suzuki Reactions in Water
J.-F. Wei, J. Jiao, J.-J. Feng, J. Lv, X.-R. Zhang, X.-Y. Shi, Z.-G. Chen, J. Org. Chem., 2009, 74, 5967-5974.
Synthesis of E-Alkyl Alkenes from Terminal Alkynes via Ni-Catalyzed Cross-Coupling of Alkyl Halides with B-Alkenyl-9-borabicyclo[3.3.1]nonanes
T. Di Franco, A. Epenoy, X. Hu, Org. Lett., 2015, 17, 4910-4913.
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.
Highly Active Catalyst for the Heterogeneous Suzuki-Miyaura Reaction: Assembled Complex of Palladium and Non-Cross-Linked Amphiphilic Polymer
Y. M. A. Yamada, K. Takeda, H. Takashashi, S. Ikegami, J. Org. Chem., 2003, 68, 7733-7741.
New Catalysts for Suzuki-Miyaura Coupling Reactions of Heteroatom-Substituted Heteroaryl Chlorides
A. S. Guram, X. Wang, E. E. Bunel, M. M. Faul, R. D. Larsen, M. J. Martinelli, J. Org. Chem., 2007, 72, 5104-5112.
A family of indolyl phosphine ligands was applied to Suzuki-Miyaura cross-coupling of aryl tosylates with boronic acids, trifluoroborate salts, and boronate esters. Catalyst loading can be reduced to 0.2 mol % for the coupling of nonactivated aryl tosylates.
C. M. So, C. P. Lau, A. S. C. Chan, F. Y. Kwong, J. Org. Chem., 2008, 73, 7731-7734.
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 use of bisphosphine ligands with a large P-Pd-P bite angle allowed to synthesize Z-chlorinated internal alkenes in good yields by a selective Suzuki-Miyaura monocoupling process of 9-alkyl-9-BBN with 1,1-dichloro-1-alkenes. These monochlorinated olefins could be further transformed providing stereospecifically trisubstituted olefins.
F. Liron, C. Fosse, A. Pernolet, E. Roulland, J. Org. Chem., 2007, 72, 2220-2223.
Stereoselective Cross-Coupling Reaction of 1,1-Diboryl-1-alkenes with Electrophiles: A Highly Stereocontrolled Approach to 1,1,2-Triaryl-1-alkenes
M. Shimizu, C. Nakamaki, K. Shimono, M. Schelper, T. Kurahashi, T. Hiyama, J. Am. Chem. Soc., 2005, 127, 12506-12507.
Pd/NHC-Catalyzed Enantiospecific and Regioselective Suzuki-Miyaura Arylation of 2-Arylaziridines: Synthesis of Enantioenriched 2-Arylphenethylamine Derivatives
Y. Takeda, Y. Ikeda, A. Kuroda, S. Tanaka, S. Minataka, J. Am. Chem. Soc., 2014, 136, 8544-8547.