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Synthesis of heterobiaryls

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A wide range of aryl boronic 1,1,2,2-tetraethylethylene glycol esters [ArB(Epin)s] were readily synthesized. ArB(Epin) derivatives are easily purified on silica gel and isolated in excellent yields. Suzuki-Miyaura couplings of ArB(Epin) derivatives provided higher yields of the desired biaryl products than those obtained using the corresponding aryl boronic acids or pinacol esters.
N. Oka, T. Yamada, H. Sajiki, S. Akai, T. Ikawa, Org. Lett., 2022, 24, 3510-3514.

Highly stable and active Pd-phosphine catalysts have been found for the Suzuki-Miyaura coupling of pyridine, pyrrole, and indole boronic acids. These complexes are not inhibited by the presence of highly basic aminopyridines or aminopyrimidines.
K. L. Billingsley, K. W. Anderson, S. L. Buchwald, Angew. Chem. Int. Ed., 2006, 45, 3484-3488.

Pd-catalyzed couplings of several (hetero)aromatic halides with (hetero)aromatic boronic acids can be conducted under mild conditions in pure water using commercially available Pd catalysts and PTS, a nanomicelle-forming amphiphile.
B. H. Lipshutz, A. R. Abela, Org. Lett., 2008, 10, 5329-5332.

A versatile microwave-assisted procedure for the palladium-catalyzed direct arylation of heterocycles by aryl bromides and heteroaryl bromides features short coupling times (10–60 min) and low catalyst loadings and allows the successful arylation of previously unreactive heterocyclic substrates.
M. Baghbanzadeh, C.Pilger, C. O. Kappe, J. Org. Chem., 2011, 76, 8138-8142.

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 highly electron-rich Pd complex efficiently catalyzes a direct arylation of heteroaromatics with unreactive and sterically hindered aryl chlorides.
D. Ghosh, H. M. Lee, Org. Lett., 2012, 14, 5534-5537.

Pinacol boronate esters that are analogous to unstable boronic acids are formed in high yield by iridium-catalyzed C-H borylation of heteroarenes and fluoroarenes. These boronates are stable in the solid state or in solution and can be generated and used in situ for the palladium-catalyzed synthesis of biaryls and heterobiaryls from arenes and haloarenes.
D. W. Robbins, J. F. Hartwig, Org. Lett., 2012, 14, 4266-4269.

An efficient palladium-catalyzed direct arylation of 2-furaldehyde with aryl halides provides a range of 5-aryl-2-formylfuran derivatives in good yields under mild conditions.
M. S. McClure, B. Glover, E. McSorley, A. Millar, M. H. Osterhout, F. Roschangar, Org. Lett., 2001, 3, 1677-1680.

N-Protected (1H-tetrazol-5-yl)zinc pivalates are storable solids with appreciably air and moisture stability. They are obtained in high yields by deprotonation using the mixed zinc-magnesium base TMPZnClˇMg(OPiv)2. Subsequent cross-couplings and copper-catalyzed electrophilic aminations using hydroxylamine benzoates give access to functionalized 1H-tetrazoles.
C. P. Tüllmann, S. Steiner, P. Knochel, Synthesis, 2020, 52, 2357-2363.

A new method for a direct, copper-catalyzed arylation of heterocycle C-H bonds by aryl iodides allows the conversion of electron-rich five-membered heterocycles and electron-poor pyridine oxides. The best results are obtained by using a combination of lithium tert-butoxide as base and copper iodide as catalyst.
H.-Q. Do, O. Daugulis, J. Am. Chem. Soc., 2007, 129, 12404-12405.

Pd(PPh3)4 efficiently catalyses both direct arylation and alkenylation of oxazoles. The method is regio- and stereospecific with respect to bromoalkenes and tolerates a wide range of functional groups.
F. Besseličvre, S. Lebrequier, F. Mahuteau-Betzer, S. Piguel, Synthesis, 2009, 3511-3512.

A straightforward route allows the synthesis of 2-(hetero)arylated and 2,5-di(hetero)arylated oxazoles through regiocontrolled palladium-catalyzed direct (hetero)arylation of ethyl oxazole-4-carboxylate with iodo-, bromo-, and chloro(hetero)aromatics.
C. Verrier, T. Martin, C. Hoarau, F. Marsais, J. Org. Chem., 2008, 73, 7383-7386.

A new catalyst system for the Pd-catalyzed cross-coupling of organozinc reagents with aryl halides permits efficient preparation of hindered biaryls, functions effectively at low levels of catalyst, and tolerates a wide range of functional groups and heterocyclic substrates.
J. E. Milne, S. L. Buchwald, J. Am. Chem. Soc., 2004, 126, 13028-13032.

New air-stable PdCl2{PR2(Ph-R')}2 complexes, readily prepared from commercial reagents, exhibit unique efficiency as catalysts for the Suzuki-Miyaura coupling reactions of a variety of heteroatom-substituted heteroaryl chlorides with a diverse range of aryl/heteroaryl boronic acids.
A. S. Guram, X. Wang, E. E. Bunel, M. M. Faul, R. D. Larsen, M. J. Martinelli, J. Org. Chem., 2007, 72, 5104-5112.

The use of well-defined and highly reactive [Pd(IPr)(3-CF3-An)Cl2] (An = aniline) or [Pd(IPr)(cin)Cl] (cin = cinnamyl) Pd(II)-NHC catalysts enables a a Suzuki-Miyaura cross-coupling of 2-pyridyl ammonium salts to furnish valuable biaryl and heterobiarylpyridines with exceptionally broad scope that are ubiquitous in medicinal chemistry and agrochemistry research.
Y. Hu, Y. Gao, J. Ye, Z. Ma, J. Feng, X. Liu, P. Lei, M. Szostak, Org. Lett., 2023, 25, 2975-2980.

New air-stable palladium phosphine complexes represent simple, general, and efficient catalysts for the Suzuki-Miyaura cross-coupling of aryl halides including five-membered heteroaryl halides and heteroatom-substituted six-membered heteroaryl chlorides with various arylboronic acids.
A. S. Guram, A. O. King, J. G. Allen, X. Wang, L. B. Schenkel, J. Chan, E. E. Bunel, M. M. Faul, R. D. Larsen, M. J. Martinelli, P. J. Reider, Org. Lett., 2006, 8, 1787-1789.

The use of Pd2(dba)3 and X-Phos as a ligand enables a mild Negishi cross-coupling of 2-heterocyclic organozinc reagents and aryl chlorides providing 2-aryl-substituted pyridines and thiophenes in high yields. An efficient method to generate the organozinc reagents at room temperature is also demonstrated.
M. R. Luzung, J. S. Patel, J. Yin, J. Org. Chem., 2010, 75, 8330-8332.

Suzuki reactions of electron-deficient 2-heterocyclic boronates generally give low conversions and remain challenging. A successful copper(I) facilitated Suzuki coupling of 2-heterocyclic boronates is broad in scope and affords greatly enhanced yields of these notoriously difficult couplings. Furthermore, mechanistic investigations suggest a possible role of copper in the catalytic cycle.
J. Z. Deng, D. V. Paone, A. T. Ginnetti, H. Kurihara, S. D. Dreher, S. A. Weissman, S. R. Stauffer, C. S. Burgey, Org. Lett., 2009, 11, 345-347.

A Suzuki-Miyaura cross-coupling of tetrabutylammonium 2-pyridyltriolborate salts with various aryl and heteroaryl chlorides produces the corresponding desired coupling products with good to excellent yields in the presence of catalytic amounts of PdCl2dcpp and CuI/MeNHCH2CH2OH in anhydrous DMF without bases. Tetrabutylammonium 2-pyridyltriolborate salts are more reactive than the corresponding lithium salts.
S. Sakashita, M. Takizawa, J. Sugai, H. Ito, Y. Yamamoto, Org. Lett., 2013, 15, 4308-4311.

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.

Air-stable and easily accessible PinP(O)H enables highly efficient palladium-catalyzed Kumada cross-coupling reactions of aryl tosylates. The in situ generated catalyst proved applicable not only to electron-rich and electron-poor carbocyclic tosylates but also to heterocyclic tosylates, such as pyridine and quinoline derivatives.
L. Ackermann, A. Althammer, Org. Lett., 2006, 8, 3457-3460.

C-C Coupling Reactions of Aryl Bromides and Arylsiloxanes in Water Catalyzed by Palladium Complexes of Phosphanes Modified with Crown Ethers
I. Gordillo, E. de Jesús, C. López-Mardomingo, Org. Lett., 2006, 8, 3517-3520.

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.

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.

A highly efficient method for the synthesis of multisubstituted 1,2,3-triazoles via a direct Pd-catalyzed C-5 arylation has been developed.
S. Chuprakov, N. Chernyak, A. S. Dudnik, V. Gevorgyan, Org. Lett., 2007, 9, 2333-2336.

The use of nontoxic polyethylene glycol (PEG) as solvent and MesCO2H as cocatalyst enabled user-friendly palladium(0)-catalyzed C-H bond functionalizations under air in the absence of phosphine ligands. Direct arylations of 1,2,3-triazoles gave substituted triazoles in good yields. Recycling of the catalytic system led to a slight decrease of activity.
L. Ackermann, R. Vicente, Org. Lett., 2009, 11, 4922-4925.

Cascade reactions starting from isocyanides allow a straightforward synthesis of five-membered ring heterocycles. Addition of sodium azide on isocyanide dibromides followed by electrocyclization and a Suzuki coupling affords tetrazoles scaffolds, whereas addition of tetrazoles on isocyanide dibromides followed by Huisgen rearrangement and a Suzuki coupling gives triazoles scaffolds.
L. El Kaim, L. Grimaud, P. Patil, Org. Lett., 2011, 13, 1261-1263.

An efficient, practical, and highly regioselective direct palladium-catalyzed C-3 arylation of electron-rich free (NH)-indoles with various aryl bromides under ligandless conditions in refluxing toluene in the presence of K2CO3 as the base can be run outside a glovebox without purification of solvent and reagents.
F. Bellina, F. Benelli, R. Rossi, J. Org. Chem., 2008, 73, 5529-5535.

A well-defined NHC-Pd(II)-Im complex enables a facile and alternative methodology for the direct C-H bond arylation of (benz)imidazoles with (hetero)aryl chlorides. Various activated, unactivated, and deactivated (hetero)aryl chlorides were used as arylating reagents to yield 2-(hetero)aryl (benz)imidazoles in good yields.
Z.-S. Gu, W.-X. Chen, L-X. Shao, J. Org. Chem., 2014, 79, 5806-5811.

A mild, Pd(OAc)2-catalyzed regioselective cross-coupling between indoles and potassium aryltrifluoroarylborates gives 2-aryl indoles in moderate yields in the presence of Cu(OAc)2 in acetic acid at room temperature.
J. Zhao, Y. Zhang, K. Cheng, J. Org. Chem., 2008, 73, 7428-7431.

The use of Cu(OAc)2 enables a dehydrogenative cross-coupling between two heteroarenes via disproportionation of the copper mediator. This synthetic protocol provides a concise and "green" access to unsymmetrical biheteroarenes bearing structural motifs of substantial utility in organic synthesis.
Z. F. Mao, Z. Wang, Z. Q. Xu, F. Huang, Z. K. Yu, R. Wang, Org. Lett., 2012, 14, 3854-3857.

An efficient and mild Negishi cross-coupling strategy for substituted 2,2′-bipyridines uses tetrakis(triphenylphosphine)palladium(0) as a simple, commercially available, and relatively inexpensive catalyst for both 2-bromo- and 2-chloropyridines.
U. Kiehne, J. Bunzen, H. Staats, A. Lützen, Synthesis, 2007, 1061-1069.

Various 5-substituted 2,2-bipyridines have been synthesized from substituted 2-chloropyridines through a modified Negishi cross-coupling reaction.
A. Lützen, M. Hapke, Eur. J. Org. Chem., 2002, 2292-2297.

Thiophene was regioselectively deprotonated by treatment with Bu3MgLi in THF at room temperature. The lithium arylmagnesate formed was either trapped with electrophiles or cross-coupled in a ‘one-pot’ procedure with aryl halides under palladium catalysis.
O. Bayh, H. Awad, F. Mongin, C. Hoarau, F. Trécourt, G. Quéquiner, F. Marsais, F. Blanco, B. Abarca, R. Ballesteros, Tetrahedron, 2005, 61, 4779-4784.