Synthesis of biaryls
Versatile Cross Coupling Methods:
Hiyama Coupling (R-X + R'-SiR''3)
Hiyama-Denmark Coupling (R-X + R-SiMe2OH)
Kumada Coupling (R-X + R'-MgX)
Negishi Coupling (R-X + R'-ZnX)
Stille Coupling (R-X + R'-SnR''3)
Suzuki Coupling (R-X + R'-BY3)
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.
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.
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.
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.
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.
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.
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.
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.
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 IMes∑Ni(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.
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. ÷zdemir, S. Demir, B. «etinkaya, 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.
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 new, anionic four-electron donor-based (type I) palladacycle-catalyzed sequential reaction of 2-bromobenzaldehydes with arylboronic acids based on the addition reaction, cyclization via C-H activation-oxidation sequence provides an efficient access to a variety of substituted fluorenones/indenofluorenediones from readily available starting materials.
T.-P. Liu, Y.-X. Liao, C.-H. Xing, Q.-S. Hu, Org. Lett., 2011, 13, 2452-2455.
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.