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.

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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.

Recent Literature

Alkyl-Alkyl Suzuki Cross-Couplings of Unactivated Secondary Alkyl Halides at Room Temperature
B. Saito, G. C. Fu, J. Am. Chem. Soc., 2007, 129, 9602-9603.

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.

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.

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.

Tetraphosphine/palladium catalysed Suzuki cross-coupling reactions of aryl halides with alkylboronic acids
I. Kondolff, H. Doucet, M. Santelli, Tetrahedron, 2004, 60, 3813-3818.

Suzuki-Miyaura Cross-Coupling Reactions of Primary Alkyltrifluoroborates with Aryl Chlorides
S. D. Dreher, S.-E. Lim, D. L. Sandrock, G. A. Molander, J. Org. Chem., 2009, 74, 3626-3631.

Pd(N,N-Dimethyl β-alaninate)₂ as a High-Turnover-Number, Phosphine-Free Catalyst for the Suzuki Reaction
X. Cui, T. Qin, J.-R. Wang, L. Liu, Q.-X. Guo, Synthesis, 2007, 393-399.

Guanidine/Pd(OAc)₂-Catalyzed Room Temperature Suzuki Cross-Coupling Reaction in Aqueous Media under Aerobic Conditions
S. Li, Y. Lin, J. Cao, S. Zhang, J. Org. Chem., 2007, 72, 4067-4072.

A Cyclobutene-1,2-Bis(imidazolium) Salt as Efficient Precursor of Palladium-Catalyzed Room-Temperature Suzuki-Miyaura Reactions
A. Rahimi, A. Schmidt, Synlett, 2010, 1327-1330.

An Extremely Active and General Catalyst for Suzuki Coupling Reaction of Unreactive Aryl Chlorides
D.-H. Lee, M.-J. Jin, Org. Lett., 2011, 13, 252-255.

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.

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.

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.

Room-Temperature Suzuki-Miyaura Couplings in Water Facilitated by Nonionic Amphiphiles
B. H. Lipshutz, T. B. Petersen, A. R. Abela, Org. Lett., 2008, 10, 1333-1336.

Solvent-Free Microwave-Assisted Suzuki-Miyaura Coupling Catalyzed by PEPPSI-iPr
P. Nun, J. Martinez, F. Lamaty, Synlett, 2009, 1761-1764.

Cross-Coupling and Dehalogenation Reactions Catalyzed by (N-Heterocyclic carbene)Pd(allyl)Cl Complexes
O. Navarro, H. Kaur, P. Mahjoor, S. P. Nolan, J. Org. Chem., 2004, 69, 3173-3180.

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.

Ferrocenyl Monophosphine Ligands: Synthesis and Applications in the Suzuki-Miyaura Coupling of Aryl Chlorides
C. Baillie, L. Zhang, J. Xiao, J. Org. Chem., 2004, 69, 7779-7782.

Reusable and Efficient Pd(OAc)₂/TBAB/PEG-400 System for Suzuki-Miyaura Cross-Coupling Reaction under Ligand-Free Conditions
W.-J. Liu, Y.-X. Xie, Y. Liang, J.-H. Li, Synthesis, 2006, 860-864.

Phosphine-Free Palladium Acetate Catalyzed Suzuki Reaction in Water
L. Liu, Y. Zhang, Y. Wang, J. Org. Chem., 2005, 70, 6122-6125.

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.

A Highly Active Catalyst for Suzuki-Miyaura Cross-Coupling Reactions of Heteroaryl Compounds
K. L. Billingsley, K. W. Anderson, S. L. Buchwald, Angew. Chem. Int. Ed., 2006, 45, 3484-3488.

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.

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.

Immobilization of Dipyridyl Complex to Magnetic Nanoparticle via Click Chemistry as a Recyclable Catalyst for Suzuki Cross-Coupling Reactions
G. Lv, W. Mai, R. Jin, L. Gao, Synlett, 2008, 1418-1422.

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.

Ligand Effects on the Stereochemical Outcome of Suzuki-Miyaura Couplings
G.-P. Lu, K. R. Voigtritter, C. Cai, B. H. Lipshutz, J. Org. Chem., 2012, 77, 3700-3703.

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.

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.

C₂-Symmetric Bis-Hydrazones as Ligands in the Asymmetric Suzuki−Miyaura Cross-Coupling
A. Bermejo, A. Ros, R. Fernández, J. M. Lassaletta, J. Am. Chem. Soc., 2008, 130, 15798-15799.

General Reaction Conditions for the Palladium-Catalyzed Vinylation of Aryl Chlorides with Potassium Alkenyltrifluoroborates
E. Alacid, C. Nájera, J. Org. Chem., 2009, 74, 8191-8195.

Stereoselective Enol Tosylation: Preparation of Trisubstituted α,β-Unsaturated Esters
J. Baxter, D. Steinhuebel, M. Palucki, I. W. Davies, Org. Lett., 2005, 7, 215-218.

N-Vinylpyridinium and -ammonium Tetrafluoroborate Salts: New Electrophilic Coupling Partners for Pd(0)-Catalyzed Suzuki Cross-Coupling Reactions
K. R. Buszek, N. Brown, Org. Lett., 2007, 9, 707-710.

Suzuki-Miyaura Cross-Coupling of Potassium Trifluoroboratohomoenolates
G. A. Molander, D. E. Petrillo, Org. Lett., 2008, 10, 1795-1798.

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.

A General Palladium Catalyst System for Suzuki-Miyaura Coupling of Potassium Aryltrifluoroborates and Aryl Mesylates
W. K. Chow, C. M. So, C. P. Lau, F. Y. Kwong, J. Org. Chem., 2010, 75, 5109-5112.

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 First General Palladium Catalyst for the Suzuki-Miyaura and Carbonyl Enolate Coupling of Aryl Arenesulfonates
H. N. Nguyen, X. Huang, S. L. Buchwald, J. Am. Chem. Soc., 2003, 125, 11818-11819.

Palladium-Catalyzed Cross-Coupling Reactions of Potassium Alkenyltrifluoroborates with Organic Halides in Aqueous Media
E. Alacid, C. Nájera, J. Org. Chem., 2009, 74, 2321-2327.

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.

Suzuki-Miyaura Cross-Coupling Reactions of Potassium Alkenyltrifluoroborates
G. A. Molander, C. R. Bernardi, J. Org. Chem., 2002, 67, 8424-8429.