Benzylation, synthesis of diarylmethanes and diarylalkanes
A metal-free carbon-carbon bond-forming coupling between tosylhydrazones and boronic acids is very general and functional-group tolerant. As the required tosylhydrazones are easily generated from carbonyl compounds, it can be seen as a reductive coupling of carbonyls, a process of high synthetic relevance that requires several steps using other methodologies.
J. Barluenga, M. Tomás-Gamasa, F. Aznar, C. Valdés, Nat. Chem., 2009, 1, 494-499.
The presence of catalytic amounts of 3-methyl-1-sulfonic acid imidazolium tetrachloroaluminate ([Msim]AlCl4) or silica sulfuric acid (SSA) enables an efficient benzylation of a range of aromatic compounds by benzyl acetate under mild conditions. Simple methodology, easy workup procedure, clean reaction and reusability of the catalyst are some advantages.
M. A. Zolfigol, H. Vahedi, S. Azimi, A. R. Moosavi-Zare, Synlett, 2013, 24, 1113-1116.
A highly efficient secondary benzylation procedure of nucleophiles (arenes, heteroarenes, alcohols, thiols, amides) with benzylic alcohols afforded the corresponding benzylated products in moderate to excellent yields in the presence of a high-valent heterobimetallic complex [Ir2(COD)2(SnCl3)2(Cl)2(μ-Cl)2] as the catalyst.
S. Podder, J. Choudhury, S. Roy, J. Org. Chem., 2007, 72, 3129-3132.
Easily reachable electron-poor/rich primary and secondary benzylic phosphates are suitably substrates for Friedel-Crafts benzylation reactions with only 1.2 equiv activated/deactivated arenes without additional solvent to access structurally and electronically diverse triarylmethanes, diarylethanes, and diarylmethanes with excellent yields and selectivities at room temperature within short reaction times.
G. Pallikonda, M. Chakravarty, J. Org. Chem., 2016, 81, 2135-2142.
An efficient Pd-catalyzed coupling of benzylic phosphates with arylsilanes provides straightforward access to diarylmethanes in very good yields. The reaction tolerates a wide range of functionalities such as halide, alkoxyl, and nitro groups.
P. Zhang, J. Xu, Y. Gao, X. Li, G. Tang, Y. Zhao, Synlett, 2014, 25, 2928-2932.
The use of 1,3-dicyclohexylimidazol-2-ylidene as a ligand enables a nickel-catalyzed cross-coupling of methoxyarenes with alkyl Grignard reagents via cleavage of the C(aryl)-OMe bond. Various alkyl groups, including Me, Me3SiCH2, ArCH2, adamantyl, and cyclopropyl can be introduced.
M. Tobisu, T. Takahira, N. Chatani, Org. Lett., 2015, 17, 4352-4355.
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.
A nickel-catalyzed cross coupling of benzylic ammonium triflates with aryl boronic acids affords diarylmethanes and diarylethanes. This reaction proceeds under mild reaction conditions and with exceptional functional group tolerance. Further, it transforms branched benzylic ammonium salts with excellent chirality transfer, offering a new strategy for the synthesis of highly enantioenriched diarylethanes.
P. Maity, D. M. Shacklady-McAtee, G. P. A. Yap, E. R. Sirianni, M. P. Watson, J. Am. Chem. Soc., 2013, 135, 280-285.
A palladium-catalyzed coupling of N,N-ditosylbenzylamines with arylboronic acids results in diarylmethanes in high yields. The N,N-ditosylimide group provided an efficient leaving group for the Pd-catalyzed benzylation of arylboronic acids.
S. Yoon, M. C. Hong, H. Rhee, J. Org. Chem., 2014, 79, 4206-4207.
A magnesium-mediated reductive cross-coupling between benzyl chlorides and aryl chlorides or fluorides gives diarylmethanes in good to excellent yields in a one-pot manner using easy-to-access mixed PPh3/NHC Ni(II) complexes of Ni(PPh3)(NHC)Br2 as catalyst precursors.
J. Zhang, G. Lu, J. Xu, H. Sun, Q. Shen, Org. Lett., 2016, 18, 2860-2863.
The reaction of benzylic chlorides with Al-powder in the presence of InCl3 as catalyst provides various functionalized benzylic aluminum sesquichlorides under mild conditions. These organometallics reacted smoothly in Pd-catalyzed cross-couplings, or Cu-mediated acylations, allylations, or 1,4-addition reactions. Substrates prone to Wurtz coupling can be converted to benzylic zinc compounds first.
T. D. Blümke, K. Gross, K. Karaghiosoff, P. Knochel, Org. Lett., 2011, 13, 6440-6443.
Diarylmethanes can be accessed efficiently by Suzuki-Miyaura cross-couplings of arylboronic acids with benzyl halides mediated by trans-PdBr(N-Succ)(PPh3)2. The methodology can be applied to the synthesis of heteroaryl analogues.
I. J. S. Fairlamb, P. Schnal, R. J. K. Taylor, Synthesis, 2009, 508-510.
The palladium-catalyzed cross-coupling of various benzylic carbonates with arylboronic acids gave the corresponding diarylmethanes in high yields. The catalyst is generated in situ from [Pd(η3-C3H5)Cl]2 and 1,5-bis(diphenylphosphino)pentane (dpppe).
R. Kuwano, M. Yokogi, Org. Lett., 2005, 7, 945-947.
A cross-coupling reaction of various aryl, heteroaryl, and benzyl chlorides with ArMgX is catalyzed by nickel in the presence of a bidentate phosphine ligand. The ligand is stable in air and forms a stable complex in situ upon reaction with Ni(CH3CN)2Cl2.
R. Ghosh, A. Sarkar, J. Org. Chem., 2010, 75, 8283-8386.
A ligand-controlled nickel migration/arylation enables a highly efficient remote reductive cross-electrophile coupling. This general protocol allows the use of abundant and bench-stable alkyl bromides and aryl bromides for the synthesis of a wide range of structurally diverse 1,1-diarylalkanes in excellent yields and high regioselectivities under mild conditions.
F. Chen, K. Chen, Y. Zhang, Y. He, Y.-M. Wang, S. Zhu, J. Am. Chem. Soc., 2017, 139, 13929-13935.
Judicious choice of ligand for both copper(I) hydride and palladium catalysis enabled a hydroarylation protocol to work for an extensive array of aryl bromides and styrenes, including β-substituted vinylarenes and six-membered heterocycles, under relatively mild conditions.
S. D. Friis, M. T. Pirnot, S. L. Buchwald, J. Am. Chem. Soc., 2016, 138, 8372-8375.
The use of the Xantphos ligand in a mild palladium-catalyzed Kumada-Corriu reaction of secondary benzylic bromides with aryl and alkenyl Grignard reagents minimizes the undesired β-elimination pathway. The corresponding cross-coupling products can be isolated in good yields with inversion of the configuration.
A. López-Pérez, J. Adrio, J. C. Carretero, Org. Lett., 2009, 11, 5514-5517.
An efficient Hiyama coupling reaction between benzylic halides and aryltrialkoxysilanes using Pd nanoparticles allows the synthesis of a diverse range of diarylmethanes which are ubiquitous units of natural products and pharmaceuticals.
D. Srimani, A. Bej, A. Sarkar, J. Org. Chem., 2010, 75, 4296-4299.
Suzuki-Miyaura cross-coupling of benzylic phosphates with arylboronic acids using a simple catalytic system of palladium(II) acetate and triphenylphosphine with either potassium phosphate or potassium carbonate as the base and toluene as the solvent at 90°C allows the preparation of a series of structurally diverse diarylmethanes.
M. McLaughlin, Org. Lett., 2005, 7, 4875-4878.
Coupling of sterically hindered aryl and activated alkyl chlorides bearing β-hydrogens has been successfully achieved by using N-heterocyclic carbene (NHC)Pd-carboxylate complexes as catalysts.
R. Singh, M. S. Viciu, N. Kramareva, O. Navarro, S. P. Nolan, Org. Lett., 2005, 7, 1829-1832.
A new, reusable Pd/MgLa mixed oxide catalyst has been applied successfully in the Suzuki-Miyaura cross-coupling reaction of aryl halides as well as benzylic bromide with boronic acids in ethanol. The catalyst is air stable, can be stored and handled under an ambient atmosphere and after the reaction it can be recovered by simple filtration and reused without significant loss of activity.
A. Cwik, Z. Hell, F. Figueras, Org. Biomol. Chem., 2005, 3, 4307-4309.
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.
A combination of copper chloride, triethyl phosphite, and tetrabutylammonium iodide is a very efficient catalytic system for cross-coupling reaction of arylmagnesium halides with benzylic phosphates.
C. C. Kofink, P. Knochel, Org. Lett., 2006, 8, 4121-4124.
A hybrid catalyst of iron oxide nanoparticles on carboxy-functionalized graphite demonstrated superior catalytic activity towards the alkylation of arenes with alkyl halides in contrast to commercial graphite or unsupported iron oxide nanoparticles. The catalyst can be reused up to five times with a minimal loss of catalytic activity.
V. Rajpara, S. Banerjee, G. Sereda, Synthesis, 2010, 2835-2840.
A novel InCl3/SiO2-catalyzed hydroarylation of various styrenes with arenes can be carried out under solvent-free conditions to afford a series of 1,1-diarylalkanes in high yields and with good regioselectivities. The catalyst can be reused six times without obvious loss of catalytic activity.
G. Sun, H. Sun, Z. Wang, M.-M. Zhou, Synlett, 2008, 1096-1100.
A high-yielding, and scalable deprotonative-cross-coupling process (DCCP) for palladium-catalyzed C(sp3)-H arylation of simple diarylmethane derivatives with aryl bromides can be conducted at room temperature. This method facilitates access to a variety of sterically and electronically diverse hetero- and nonheteroaryl-containing triarylmethanes, a class of compounds with various applications and interesting biological activity.
J. Zhang, A. Bellomo, A. D. Creamer, S. D. Dreher, P. J. Walsh, J. Am. Chem. Soc., 2012, 134, 13765-13772.
Palladium-catalyzed reductive coupling reactions between N-tosylhydrazones and aryl halides provide a general route for the synthesis of triarylmethanes.
Y. Xia, F. Hu, Z. Liu, P. Qu, R. Ge, C. Ma, Y. Zhang, J. Wang, Org. Lett., 2013, 15, 1784-1787.
Suzuki-Miyaura coupling of diarylmethyl carbonates with arylboronic acids gives various triarylmethanes in the presence of [Pd(η3-C3H5)Cl]2−DPPPent (1,5-bis(diphenylphosphino)pentane) as catalyst.
J.-Y. Yu, R. Kuwano, Org. Lett., 2008, 10, 973-976.
Arylboration of vinylarenes and methyl crotonate with aryl halides and bis(pinacolato)diboron by cooperative Pd/Cu catalysis gives 2-boryl-1,1-diarylethanes and α-aryl-β-boryl ester in a regioselective manner. The reaction is compatible with various functionalities and can be scaled-up to a gram scale.
K. Semba, Y. Nakao, J. Am. Chem. Soc., 2014, 136, 7567-7570.
Sm(OTf)3 is an effective catalysts for a versatile and efficient halogen-promoted highly regio- and stereoselective Friedel-Crafts (F-C) alkylation of electron-rich arenes with alkenes and α,β-unsaturated carbonyl compounds in the presence of NBS or I2 as halogen sources.
S. Haira, B. Maji, S. Bar, Org. Lett., 2007, 9, 2783-2786.
The superacid-catalyzed reaction of various olefinic amines and related compounds with benzene gives addition products in good yields. The formation of reactive, dicationic electrophiles is proposed.
Y. Zhang, A. McElrea, G. V. Sanchez, Jr., D. Do, A. Gomez, S. L . Aguirre, R. Rendy, D. A. Klumpp, J. Org. Chem., 2003, 68, 5119-5122.
The reaction of different functionalised organolithium compounds prepared by DTBB-catalysed lithiation of isochromane, phthalane, 2,3-dihydrobenzofuran and 1-chloro-3,3-diethoxypropane with an equimolecular amount of zinc bromide, followed by reaction with an aryl or an alkenyl bromide in the presence of a palladium catalyst gives the expected cross-coupling products.
M. Yus, J. Gomis, Eur. J. Org. Chem., 2002, 1989-1995.