Categories: C-C Bond Formation > Arenes >
Synthesis of biaryls
Versatile Cross Coupling Methods:
A palladium-catalyzed direct cross-coupling of aryl chlorides with a wide range of (hetero)aryl lithium compounds in the presence of Pd-PEPPSI-IPent or Pd2(dba)3/XPhos as the catalyst enables the preparation of biaryl and heterobiaryl compounds in high yields under mild conditions with short reaction times.
V. Hornillos, M. Giannerini, C. Vila, M. Fańanás-Mastral, B. L. Feringa, Org. Lett., 2013, 15, 5114-5117.
In a simple and efficient direct radical arylation of unactivated arenes, cheap and commercially available phenyl hydrazine is used as an initiator. The reaction occurs through a base promoted homolytic aromatic substitution (BHAS) mechanism via aryl radicals and aryl radical anions as intermediates and offers a practical approach for preparation of an array of substituted biaryls.
A. Dewanji, S. Murarka, D. P. Curran, A. Studer, Org. Lett., 2013, 15, 6102-6105.
8-Hydroxyquinoline promotes a transition-metal-free direct C-H arylation of unactivated arenes with aryl bromides to provide biaryl compounds with structural diversity in good yields. Mechanistic studies reveal that the reaction proceeds via a homolytic aromatic substitution pathway.
X. Zheng, X.-N. Wu, J.-Y. Chen, H.-B. Luo, D. Wu, Y. Wu, Synthesis, 2018, 50, 1721-1727.
A universal, bench-stable and easily prepared NiIICl(1-naphthyl)(PCy3)2/PCy3 σ-complex enables efficient and quantitative cross-coupling of aryl chlorides, bromides, iodides, mesylates, and fluorides with aryl neopentylglycolboronates.
J. Malineni, R. L. Jezorek, N. Zhang, V. Percec, Synthesis, 2016, 48, 2795-2807.
An efficient CuI-catalyzed Suzuki-Miyaura reaction for the coupling of aryl- and heteroarylboronate esters with aryl and heteroaryl iodides proceeds at low catalyst loadings and for aryl-heteroaryl and heteroaryl-heteroaryl couplings under ligand-free conditions. Mechanistic studies demonstrated that [(L)CuF]2 is the species that undergoes transmetalation with arylboronate esters.
S. K. Gurung, S. Thapa, A. Kafle, D. A. Dickie, R. Giri, Org. Lett., 2014, 16, 1264-1267.
Poly(2-aminothiophenol)-stablized gold nanoparticles with proper gold size and polymer thickness are active catalysts for Suzuki-Miyaura cross-coupling reaction of aryl halides with arylboronic acids in water and air. High yields can be obtained with aryl halides or arylboronic acids bearing various substituents. The catalyst can be recycled.
J. Han, Y. Liu, R. Guo, J. Am. Chem. Soc., 2009, 131, 2060-2061.
Palladium immobilized on a sulfur-modified gold surface (SAPd) offers a high recyclability. Because this material leaches extremely low levels of Pd into the reaction mixture, removal of the residual Pd is unnecessary using SAPd, even in syntheses involving pharmaceutical ingredients.
N. Hoshiya, M. Shimoda, H. Yoshikawa, Y. Yamashita, S. Shuto, M. Arisawa, J. Am. Chem. Soc., 2010, 132, 7270-7272.
In a mechanical Suzuki-Miyaura reaction of aryl chlorides, an unexpected improvement of yield is observed using alcohols as additives, which is explained by in situ formed alkoxides and their participation in oxidative addition. Liquid-assisted grinding with a Pd(OAc)2/PCy3/MeOH system provides desired products in very good yields.
Z.-J. Jiang, Z.-H. Li, J.-B. Yu, W.-K. Su, J. Org. Chem., 2016, 81, 10049-10055.
Poly(vinyl chloride)-supported nanoparticles of metallic palladium enable an efficient Suzuki reaction at room temperature. Aryl iodides, bromides, and chlorides underwent smooth reactions in aqueous ethanol under ligand-free conditions to give good yields of the desired biaryl products. The heterogeneous catalyst could be used up to four times with no detectable metal leaching or loss of catalytic efficiency.
M. Samarasimhareddy, G. Prabhu, T. M. Vishwanatha, V. V. Sureshbabu, Synthesis, 2013, 45, 1201-1206.
A complex generated from iron(III) fluoride and 1,3-bis(2,6-di-i-propylphenyl)imidazolinium chloride catalyzes the reaction of aryl magnesium bromides with aryl chlorides to give the corresponding cross-coupling products, unsymmetrical biaryls, in good to excellent yields.
T. Hatakeyama, M. Nakamura, J. Am. Chem. Soc., 2007, 129, 9844-9845.
The evaluation of a small, rationally designed library of NHC-palladacycles showed, that combining the bulky N-heterocyclic carbene (NHC) 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr) with cyclopalladated acetanilide as the optimal palladium precatalyst leads to superior catalytic activity in sp2-sp2, sp2-sp3 and sp3-sp3 Suzuki-Miyaura coupling reactions.
G.-R. Peh, E. A. B. Kantchev, J.-C. Er, J. Y. Ying, Chem. Eur. J., 2010, 14, 4010-4017.
An efficient, palladium-catalyzed Hiyama cross-coupling reaction of aryltrifluorosilanes with aryl chlorides enables the preparation of various functionalized biaryl derivatives in good to excellent yields. The scope of this reaction has also been extended to heteroaryl chlorides, affording the corresponding heterobiaryl compounds in high yields.
G. A. Molander, L. Iannazzo, J. Org. Chem., 2011, 76, 9102-9108.
Aryltriethoxysilanes were cross-coupled with aryl bromides in high yield in the presence of a palladium catalyst and aqueous sodium hydroxide. Addition of P(OiPr)3 helps to prevent the precipitation of palladium black.
M. Murata, R. Shimazaki, S. Watanabe, Y. Masuda, Synthesis, 2001, 2231-2233.
N-Heterocyclic Carbene/Pd(II)/1-Methylimidazole Complex Catalyzed Suzuki-Miyaura Coupling Reaction of Aryl Chlorides in Water
X.-X. Zhou, L.-X. Shao, Synthesis, 2011, 3138-3142.
Room-temperature Ni(0)-catalyzed cross-coupling reactions of deactivated aryl chlorides with arylboronic acids with inexpensive triphenylphosphine as ligand have been accomplished in good to excellent yields. Highly active nickel catalysts were obtained through the reduction of air-stable Ni(PPh3)2Cl2 with n-BuLi in the presence of an aryl chloride.
Z.-Y. Tang, Q.-S. Hu, J. Org. Chem., 2006, 71, 2167-2169.
A new class of easily accessible indolyl phosphine ligands provides high potential of steric and electronic tunability. The air-stable indolyl phosphines in combination with a palladium metal precursor are effective catalysts for Suzuki-Miyaura coupling of unactivated aryl chlorides, and a catalyst loading down to 0.02 mol % can be achieved.
C. M. So, C. P. Lau, F. Y. Kwong, Org. Lett., 2007, 9, 2795-2798.
A catalytic amount of a complex of a diphenylvinylphosphine ligand and palladium efficiently mediates the reactions of a variety of aryl halides with arylboronic acids to afford the corresponding biphenyls in good to excellent yields.
K. Suzuki, A. Fontaine, Y. Hori, T. Kobayashi, Synlett, 2007, 3206-3207.
High-yielding Kumada couplings can occur in the presence of many electrophilic and heterocyclic functional groups if oxidative addition rates are matched with the rate of syringe pump addition of the Grignard reagent.
X. Hua, J. M. Makdissi, R. J. Sullivan, S. G. Newman, Org. Lett., 2016, 18, 5312-5315.
Hydroxyphosphine ligands (PO ligands) significantly accelerate nickel-catalyzed cross-coupling reactions of Grignard reagents with unreactive aryl electrophiles such as fluorides, chlorides, carbamates and phosphates to give the corresponding cross-coupling products in good to excellent yields.
N. Yoshikai, H. Matsuda, E. Nakamura, J. Am. Chem. Soc., 2009, 131, 9590-9599.
The selectivity challenge associated with cross-coupling of aryl chlorides as inert electrophiles with aryl triflates as reactive ones is overcome using a multimetallic strategy with the appropriate choice of additive. LiCl is essential for effective cross-coupling by accelerating the reduction of Ni(II) to Ni(0) and counteracting autoinhibition of reduction at Zn(0) by Zn(II) salts.
L. Huang, L. K. G. Ackerman, K. Kang, A. M. Parsons, D. J. Weix, J. Am. Chem. Soc., 2019, 141, 10978-10983.
The combination of a Ni and Pd complex with Zn as reductant and LiBr as an additive catalyzed a direct cross-coupling of two different sulfonate esters. Whereas Pd strongly prefers the aryl triflate, the Ni catalyst has a small preference for the aryl tosylate, aryl transfer between catalysts is mediated by Zn, and Pd improves yields by consuming arylzinc intermediates.
K. Kang, L. Huang, D. J. Weix, J. Am. Chem. Soc., 2020, 142, 10634-10640.
A simple and efficient palladium-catalyzed reaction of aryl chlorides with tetrahydroxydiboron gives arylboronic acids. To ensure preservation of the carbon-boron bond, the boronic acids were efficiently converted in situ to trifluoroborate derivatives or boronates in very good yields. Finally, a two-step, one-pot method for the synthesis of biaryls from two aryl chlorides was developed.
G. A. Molander, S. L. J. Trice, S. D. Dreher, J. Am. Chem. Soc., 2010, 132, 17701-17703.
Transmetalation between lithium compounds and a significantly improved insoluble polymer-supported siloxane-transfer agent permits subsequent, efficient palladium-catalyzed cross-coupling reactions. The cross-linked polystyrene support facilitates product purification with excellent siloxane recycling.
M. H. Nguyen, A. B. Smith, III, Org. Lett., 2014, 16, 2070-2073.
A reusable silicon-based transfer agent enables effective room-temperature palladium-catalyzed cross-coupling reactions (CCRs) of aryl and heteroaryl chlorides with readily accessible aryl lithium reagents. The crystalline, bench-stable siloxane transfer agent is easily prepared via a one-step protocol. Importantly, this green CCR protocol generates LiCl as the only stoichiometric waste.
D. Martinez-Solorio, B. Melillo, L. Sanchez, Y. Liang, E. Lam, K. N. Houk, A. B. Smith, III, J. Am. Chem. Soc., 2016, 138, 1836-1839.
An efficient copper(I) iodide catalyzed cross-coupling of diarylzinc reagents with aryl iodides proceeds under ligand-free conditions at low catalyst loading (5 mol%) and tolerates various functional groups.
S. Thapa, A. S. Vangala, R. Giri, Synthesis, 2016, 48, 504-511.
Cross-Coupling of ArX with ArMgBr Catalyzed by N-Heterocyclic Carbene-Based Nickel Complexes
W.-J. Guo, Z.-X. Wang, J. Org. Chem., 2013, 78, 1054-1061.
Addition of a phenolate to FeCl3/Ti(OEt)4/TMEDA enables a strong Fe/Ti cooperativity that can efficiently catalyze a general and selective biaryl coupling reaction in the absence of ligands. Various aryl iodides, bromides, and chlorides can be coupled with a variety of common and Knochel-type aryl Grignard reagents. A wide range of sensitive functional groups in either coupling partner are tolerated.
R. Zhang, Y. Zhao, K.-M. Liu, X.-F. Duan, Org. Lett., 2018, 20, 7942-7946.
Nickel-catalyzed cross-coupling of Grignard reagents with aryl fluorides or chlorides can be achieved efficiently in the presence of a new triarylphosphine ligand. The high reactivity and the unique chemoselectivity of the catalysis have been attributed to synergy of nickel and magnesium atoms preorganized on the ligand.
N. Yoshikai, H. Mashima, E. Nakamura, J. Am. Chem. Soc., 2005, 127, 17978-17979.
Ni(PCy3)2Cl2 effectively catalyzes cross-coupling of aryl fluorides and organozinc reagents. Both electron-poor and -rich aryl fluorides can react effectively with nucleophiles including aryl-, methyl-, and benzylzinc chlorides. A wide range of substituents and functional groups are tolerated.
F. Zhu, Z.-X. Wang, J. Org. Chem., 2014, 79, 4285-4292.
Diaryl-, divinyl-, and dialkylindium compounds undergo a palladium-catalyzed cross-coupling reaction with aryl halides in aqueous THF to provide the corresponding coupling product in excellent yield. A wide range of functional groups are tolerated. The indium compounds can be generated from indium trichloride and two equimolar amounts of a Grignard reagent.
K. Takami, H. Yorimitsu, H. Shinokubo, S. Matsubara, K. Oshima, Org. Lett., 2001, 3, 1997-1999.
In situ nonaflation of phenols using nonafluorobutanesulfonyl fluoride (NfF) enables Palladium-catalyzed coupling reactions, such as the Suzuki-Miyaura, Sonogashira, Stille, and Buchwald-Hartwig couplings.
T. Ikawa, K. Saito, S. Akai, Synlett, 2012, 23, 2241-2246.
Low loadings of (IPr)Ni(allyl)Cl catalyzes the cross-coupling reactions of heteroaromatic chlorides with aryl Grignard reagents to afford products in excellent yields. This nickel-based catalytic system also promotes the activation of the CAr-O bond of anisoles in the Kumada-Tamao-Corriu reaction under fairly mild conditions.
M. J. Iglesias, A. Prueto, M. C. Nicasio, Org. Lett., 2012, 14, 4318-4321.
The use of Ni(cod)2 in conjunction with 1,3-dicyclohexylimidazol-2-ylidene enables a cross-coupling of aryl and benzyl methyl ethers with organoboron reagents. This method not only allows for the use of readily available methyl ethers as halide surrogates but also provides a functional group tolerant method for the late-stage derivatization of complex molecules.
M. Tobisu, A. Yasutome, H. Kinuta, K. Nakamura, N. Chatani, Org. Lett., 2014, 16, 5572-5575.
Magnetic Pd-Nanoparticles catalyzes a one-pot diazotization-cross-coupling reaction of anilines and arylboronic acids to yield biaryls in good to excellent yields. The catalyst can recovered through magnetic separation and reused for three times. There were several obvious advantages such as broad applicability, high selectivity, simply experimental operation as well as the convenient preparation, high efficiency and reusability of catalyst.
Y. Zong, J. Hu, P. Sun, X. Jiang, Synlett, 2012, 23, 2393-2396.
Aryltrimethylammonium triflates and tetrafluoroborates are highly reactive electrophiles in the Pd-catalyzed cross coupling with aryl Grignard reagents. The coupling proceeds at ambient temperature with a nearly stoichiometric quantity of Grignard reagent and tolereates diverse functionality.
J. T. Reeves, D. R. Fandrick, Z. Tan, J. J. Song, H. Lee, N. K. Yee, C. H. Senanayake, Org. Lett., 2010, 12, 4388-4391.
The cross-coupling reaction of aryltrimethylammonium iodides with aryl- or heteroarylzinc chlorides is catalyzed by low loadings of amido pincer nickel complexes and displays broad substrate scope.
X.-Q. Zhang, Z.-X. Wang, J. Org. Chem., 2012, 77, 3658-3663.
In a synthesis of biaryls via the Suzuki-Miyaura coupling of nitroarenes as electrophilic coupling partners, the catalytic cycle is initiated by the cleavage of the aryl-nitro bond by palladium, which represents an unprecedented elemental reaction.
M. R. Yadav, M. Nagaoka, M. Kashihara, R.-L. Zhong, T. Miyazaki, S. Sakaki, Y. Nakao, J. Am. Chem. Soc., 2017, 139, 9423-9426.
A Suzuki-Miyaura cross-coupling of arenediazonium salts with arylboronic acids using a recyclable polymer-supported N-heterocyclic carbene-Pd complex catalyst was performed at room temperature under aerobic conditions to give biaryls in very good yields in the absence of a base. The supported catalyst could be reused several times and still retained its high activity.
Y. Qin, W. Wei, M. Luo, Synlett, 2007, 2410-2414.
Palladium-catalyzed Heck and Suzuki coupling reactions of arenediazonium salts were performed at room temperature, without added base, under aerobic conditions using a thiourea-based C2-symmetric ligand. The reactions produced product in 4 h in good yield.
M. Dai, B. Liang, C. Wang, J. Chen, Z. Yang, Org. Lett., 2004, 6, 221-224.
Synthesis of Axially Chiral 2,2′-Bisphosphobiarenes via a Nickel-Catalyzed Asymmetric Ullmann Coupling: General Access to Privileged Chiral Ligands without Optical Resolution
Z. Zuo, R. S. Kim, D. A. Watson, J. Am. Chem. Soc., 2021, 143, 1328-1333.
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.
The Suzuki-Miyaura cross-coupling of arenediazonium tetrafluoroborate salts with boronic acids catalyzed by Pd(0)/C in alcoholic solvents is a practical, mild and efficient alternative to classical homogeneous conditions. A chemoselective one-pot double cross-coupling allows the synthesis of unsymmetrical terphenyls.
R. H. Taylor, F.-X. Felpin, Org. Lett., 2007, 9, 2911-2914.
A suzuki cross-coupling reaction of aryltrimethylammonium triflates based on an IMesˇNi(0) catalyst system tolerates a wide range of electron-withdrawing and electron-donating substituents on both coupling partners. This methodology constitutes a novel, mild method to activate anilines for metal-catalyzed cross-coupling reactions.
S. B. Blakey, D. W. C. MacMillan, J. Am. Chem. Soc., 2003, 125, 6046-6047.
High-speed and scalable nickel-catalyzed cross-coupling of arylboronic acids with aryl carbamates and sulfamates is achieved by using sealed-vessel microwave processing.
M. Baghbanzadeh, C. Pilger, C. O. Kappe, J. Org. Chem., 2011, 76, 1507-1510.
Air-Stable PinP(O)H as Preligand for Palladium-Catalyzed Kumada Couplings of Unactivated Tosylates
L. Ackermann, A. Althammer, Org. Lett., 2006, 8, 3457-3460.
An efficient, palladium-catalyzed Hiyama cross-coupling reaction of aryl arenesulfonate with arylsilane proceeds under mild conditions with good functional group tolerance.
L. Zhang, J. Wu, J. Am. Chem. Soc., 2008, 130, 12250-12251.
Palladium-catalyzed Hiyama-type cross-coupling reactions of various arenesulfinates with organosilanes were achieved in high yields under aerobic conditions at 70°C in the presence of tetrabutylammonium fluoride. These cross-coupling reactions show wide functional group tolerance.
K. Cheng, S. Hu, B. Zhao, X.-M. Zhang, C. Qi, J. Org. Chem., 2013, 78, 5022-5025.
A range of biaryl compounds can be efficiently prepared in high yields by a palladium-catalyzed cross-coupling reaction between ortho-substituted triarylindium reagents and aryl halides. The triarylindium reagents are prepared by directed ortho-lithiation and transmetallation to indium from the corresponding benzene derivatives.
M. A. Pena, J. P. Sestelo, L. A. Sarandeses, J. Org. Chem., 2007, 72, 1271-1275.
Sterically demanding 1,3-dialkyl-3,4,5,6-tetrahydropyrimidinium salts as NHC precursors in combination with palladium acetate provided active catalysts for the cross-coupling of aryl chlorides and bromides under mild conditions. The catalytic system was applied to the Heck, Suzuki and benzaldehyde coupling reactions.
I. Özdemir, S. Demir, B. Çetinkaya, Tetrahedron, 2005, 61, 9791-9798.
The mild cross-coupling reaction of alkyl- and arylmanganese reagents with o-chloro- or o-bromoaryl ketones gives substituted ketones in high yields with excellent chemoselectivity.
G. Cahiez, D. Luart, F. Lecomte, Org. Lett., 2004, 6, 4395-4398.
The ortho-arylation of aromatic ketones with arylboronates using RuH2(CO)(PPh3)3 as a catalyst was conducted in pinacolone. This solvent dramatically suppressed the competing reduction of the aromatic ketones and, as a result, ortho-arylated products were obtained in high yield. The mechanism is discussed.
F. Kakiuchi, Y. Matsuura, S. Kan. N. Chatani, J. Am. Chem. Soc., 2005, 127, 5936-5945.
The use of a dual palladium/organic photoredox catalytic system enables the directed arylation of arenes with aryldiazonium salts under mild reaction conditions. This reaction serves as not only an alternative route for a broad range of biaryl motifs but also a new example for the application of an organic photoredox catalyst.
J. Jiang, W.-M. Zhang, J.-J. Dai, J. Xu, H.-J. Xu, J. Org. Chem., 2017, 82, 3622-3630.
Low-toxicity chromium(II) chloride catalyzes very fast coupling reactions of various (hetero)arylmagnesium reagents with N-heterocyclic halides, aromatic halogenated ketones or imines, and alkenyl iodides at room temperature. Remarkably, much lower amounts of homo-coupling side products are obtained compared to related iron, cobalt, or manganese cross-couplings.
A. K. Steib, O. M. Kuzmina, S. Fernandez, D. Flubacher, P. Knochel, J. Am. Chem. Soc., 2013, 135, 15346-15349.
A broad range of functionalized Grignard compounds were coupled by using diphenoquinone as an electron acceptor. The oxidative dimerization of alkenylmagnesium reagents proceeds with complete retention of the stereochemistry.
A. Krasovskiy, A. Tishkov, V. del Amo, H. Mayr, P. Knochel, Angew. Chem. Int. Ed., 2006, 45, 5010-5014.
A direct Pd-catalyzed arylation reaction for the intramolecular formation of biaryl compounds using a novel phosphine ligand offers enhanced catalytic activity for transformations of previously unreactive substrates.
L.-C. Campeau, M. Parisien, M. Leblanc, K. Fagnou, J. Am. Chem. Soc., 2004, 126, 9186-9187.