Copper-mediated arylation with arylboronic acids: Facile and modular synthesis of triarylmethanes

• H. Surya Prakash Rao and
• A. Veera Bhadra Rao

Beilstein J. Org. Chem. 2016, 12, 496–504, doi:10.3762/bjoc.12.49

• triphenylmethane (11a). A plausible mechanism for the formation of triarylmethanes 11. Copper-catalyzed C–C bond formation synthesis of triarylmethane 10l. Synthesis of anti-breast-cancer agent intermediate 22. Screening of metal catalysts for the arylation reaction. Scope of the Cu-catalyzed arylation with

N-Methylphthalimide-substituted benzimidazolium salts and PEPPSI Pd–NHC complexes: synthesis, characterization and catalytic activity in carbon–carbon bond-forming reactions

• Senem Akkoç,
• Yetkin Gök,
• İlhan Özer İlhan and
• Veysel Kayser

Beilstein J. Org. Chem. 2016, 12, 81–88, doi:10.3762/bjoc.12.9

• Pd–NHC complexes as catalysts in arylation reaction First, we performed the arylation reaction between the 4-bromoacetophenone, which is electron-deficient, with 2-n-butylthiophene without the catalyst at 110 °C for 1 h in DMAc as solvent and the reaction resulted in only a 1% yield. When we

A convergent, umpoled synthesis of 2-(1-amidoalkyl)pyridines

• Tarn C. Johnson and
• Stephen P. Marsden

Beilstein J. Org. Chem. 2016, 12, 1–4, doi:10.3762/bjoc.12.1

• substitution of suitably-activated pyridine N-oxides by azlactone nucleophiles, followed by decarboxylative azlactone ring-opening. The synthesis obviates the need for precious metal catalysts to achieve a formal enolate arylation reaction, and constitutes a formally ‘umpoled’ approach to this valuable class

Pyridylidene ligand facilitates gold-catalyzed oxidative C–H arylation of heterocycles

• Kazuhiro Hata,
• Hideto Ito,
• Yasutomo Segawa and
• Kenichiro Itami

Beilstein J. Org. Chem. 2015, 11, 2737–2746, doi:10.3762/bjoc.11.295

• strongest electron-donating N-heterocyclic carbenes, resulted in the rate acceleration of the C–H arylation reaction of heterocycles over conventional ligands such as triphenylphosphine and a classical N-heterocyclic carbene. In situ observation and isolation of the 2-pyridylidene-gold(III) species, as well

• species in the arylation reaction with AuCl(PPh3) [69]. While the IPr-gold(I) complex is known to undergo oxidation to an IPr-gold(III) species [114], its inactiveness in the current reaction indicates that the electron-donating capability is not high enough to facilitate this process. Direct observation

Recent advances in copper-catalyzed asymmetric coupling reactions

• Fengtao Zhou and
• Qian Cai

Beilstein J. Org. Chem. 2015, 11, 2600–2615, doi:10.3762/bjoc.11.280

• synthesis of chiral biphenyl diphosphine ligands by means of an intramolecular Ullmann coupling with the introduction of chiral bridged ethers. Catalytic asymmetric C–C coupling In 1929, Hurtley reported the first example of a C-arylation reaction of malonic esters with 2-bromobenzoic acid using a catalytic

• ] (Scheme 19). This method was further applied to a double N-arylation reaction for the enantioselective formation of spirobilactams by Cai et al. [49]. Through the combination of the copper-catalyzed double N-arylation and a simple in situ solid–solution phase separation, the spirobilatams were formed in

• spirobilactams through a double N-arylation reaction. Asymmetric N-arylation through kinetic resolution. Formation of cyano-substituted quaternary stereocenters through kinetic resolution. Copper-catalyzed intramolecular desymmetric aryl C–O coupling. Transition metal-catalyzed allylic substitutions. Copper

A concise and efficient synthesis of benzimidazo[1,2-c]quinazolines through CuI-catalyzed intramolecular N-arylations

• Xinlong Pang,
• Chao Chen,
• Ming Li and
• Chanjuan Xi

Beilstein J. Org. Chem. 2015, 11, 2365–2369, doi:10.3762/bjoc.11.258

• are not readily available and need harsh conditions. Herein we report a CuI-catalyzed concise and efficient method for the synthesis of benzimidazo[1,2-c]quinazoline derivatives through the intramolecular N-arylation reaction of bromo-substituted quinazolin-4(3H)-imines that are easily prepared from o

• showing the cleavage of the quinazoline ring rather than the imidazole ring [26]. Conclusion We have demonstrated a CuI-catalyzed pathway to produce functionalized benzimidazo[1,2-c]quinazoline derivatives from bromo-substituted quinazolin-4(3H)-imines through a selective intramolecular N-arylation

• reaction. The bromo-substituted quinazolin-4(3H)-imines are easily synthesized from readily available o-cyanoanilines and di-(o-bromophenyl)iodonium salt. The extension of the reaction and the investigation of the biological activity of the new products are currently under progress in our laboratory. ORTEP

Deproto-metallation of N-arylated pyrroles and indoles using a mixed lithium–zinc base and regioselectivity-computed CH acidity relationship

• Mohamed Yacine Ameur Messaoud,
• Ghenia Bentabed-Ababsa,
• Madani Hedidi,
• Aïcha Derdour,
• Floris Chevallier,
• Yury S. Halauko,
• Oleg A. Ivashkevich,
• Vadim E. Matulis,
• Laurent Picot,
• Valérie Thiéry,
• Thierry Roisnel,
• Vincent Dorcet and
• Florence Mongin

Beilstein J. Org. Chem. 2015, 11, 1475–1485, doi:10.3762/bjoc.11.160

• obtained together with recovered starting material. In order to test the functionalization of the above synthesized aryl iodides through a subsequent transition-metal-catalyzed coupling reaction we subjected three of them to a copper-catalyzed N-arylation reaction. Thus, the iodides 3b, 3d and 4d were

Advances in the synthesis of functionalised pyrrolotetrathiafulvalenes

• Luke J. O’Driscoll,
• Sissel S. Andersen,
• Marta V. Solano,
• Dan Bendixen,
• Morten Jensen,
• Troels Duedal,
• Jess Lycoops,
• Cornelia van der Pol,
• Rebecca E. Sørensen,
• Karina R. Larsen,
• Kenneth Myntman,
• Christian Henriksen,
• Stinne W. Hansen and
• Jan O. Jeppesen

Beilstein J. Org. Chem. 2015, 11, 1112–1122, doi:10.3762/bjoc.11.125

• methodology to a range of aryl halides and achieved improved yields using microwave conditions. Optimisation of this arylation reaction is ongoing in our laboratory, including its extension to BPTTFs. We are continuing to improve and exploit these synthetic routes in our studies of MPTTF and BPTTF-based

Tuning of tetrathiafulvalene properties: versatile synthesis of N-arylated monopyrrolotetrathiafulvalenes via Ullmann-type coupling reactions

• Vladimir A. Azov,
• Diana Janott,
• Dirk Schlüter and
• Matthias Zeller

Beilstein J. Org. Chem. 2015, 11, 860–868, doi:10.3762/bjoc.11.96

• in hot triethyl or trimethyl phosphite. Using the second approach [17][18][19], the aryl group is attached to the MPTTF moiety using a direct copper-mediated Ullmann-type N-arylation reaction [20][21]; this method was also used for the preparation of arylated bis-pyrrolotetrathiafulvalenes 2

• moieties directly attached to an aromatic calixarene backbone, we have chosen the copper-catalysed N-arylation reaction as a method for coupling of aromatic and MPTTF moieties with each other and successfully employed it for the preparation of two bis-MPTTF-calixarene conjugates, as well as two model low

• sensitivity of the starting material 7b, as well as for 4f due to its tendency towards oxidation. Thus, the N-arylation reaction can be readily employed with electron-rich as well as electron-deficient aromatic derivatives, as well as with thioalkyl-substituted and non-substituted MPTTFs. The successful

Rational design of cyclopropane-based chiral PHOX ligands for intermolecular asymmetric Heck reaction

• Marina Rubina,
• William M. Sherrill,
• Alexey Yu. Barkov and
• Michael Rubin

Beilstein J. Org. Chem. 2014, 10, 1536–1548, doi:10.3762/bjoc.10.158

• intermolecular Heck arylation reaction [64]. Herein we describe the full account on this investigation, including the results of the structure–activity studies and provide our insight into the origins of the enantioselectivity of this transformation and factors controlling the rate of isomerization reaction

• tested in the asymmetric arylation reaction of 2,3-dihydrofuran under various reaction conditions (Table 1). It was found that the reaction proceeded efficiently, yet with only moderate enantioselectivity, in the presence of palladium acetate and Hünig’s base (Table 1, entry 3). Interestingly, the

• corresponding catalytic systems. We envisioned that inverting the absolute configuration of the asymmetric center at C4 in the dihydrooxazole ring might potentially help to improve the enantioselectivity of the arylation reaction. Indeed, it is reasonable to propose that the inversion of the stereogenic center

Consecutive cross-coupling reactions of 2,2-difluoro-1-iodoethenyl tosylate with boronic acids: efficient synthesis of 1,1-diaryl-2,2-difluoroethenes

• Ju Hee Kim,
• Su Jeong Choi and
• In Howa Jeong

Beilstein J. Org. Chem. 2013, 9, 2470–2475, doi:10.3762/bjoc.9.286

• acids are summarized in Table 2. Direct diarylation reactions of 2 with arylboronic acids were also performed because di-coupled product 4a was formed in a mono-arylation reaction (Table 1) and also a recent work showed a successful cross-coupling reaction of nonfluorinated enol tosylates with a variety

An overview of the synthetic routes to the best selling drugs containing 6-membered heterocycles

• Marcus Baumann and
• Ian R. Baxendale

Beilstein J. Org. Chem. 2013, 9, 2265–2319, doi:10.3762/bjoc.9.265

• (Scheme 13). Removal of the acetyl protecting group under acidic conditions renders aniline 1.76 which is subsequently subjected to a Meerwein arylation reaction which occurs via diazotisation and subsequent treatment with acrylonitrile in the presence of cuprous oxide [45][46][47][48]. Alternatively, an

Gold(I)-catalyzed hydroarylation reaction of aryl (3-iodoprop-2-yn-1-yl) ethers: synthesis of 3-iodo-2H-chromene derivatives

• Pablo Morán-Poladura,
• Eduardo Rubio and
• José M. González

Beilstein J. Org. Chem. 2013, 9, 2120–2128, doi:10.3762/bjoc.9.249

• arising from the migratory cyclization against that deriving from a straight iodoalkyne arylation reaction. As for the substituents on the amine ring, more electron-donating ones gave rise to the formation of the heterocycle featuring a distribution of regioisomers that indicates less iodine shift. In

The chemistry of amine radical cations produced by visible light photoredox catalysis

• Jie Hu,
• Jiang Wang,
• Theresa H. Nguyen and
• Nan Zheng

Beilstein J. Org. Chem. 2013, 9, 1977–2001, doi:10.3762/bjoc.9.234

• sizes and acyclic amines underwent the α-arylation reaction to provide benzylic amines. The arylating reagents were benzonitriles substituted with an electron-withdrawing group. The nitrile group functioned as the leaving group. In some classes of five-membered heteroaromatics, a chloride was capable of

Palladium(II)-catalyzed Heck reaction of aryl halides and arylboronic acids with olefins under mild conditions

• Tanveer Mahamadali Shaikh and
• Fung-E Hong

Beilstein J. Org. Chem. 2013, 9, 1578–1588, doi:10.3762/bjoc.9.180

• reaction conditions.a Substrate scope in the Heck arylation reaction of phenylboronic acids with olefins.a Substrate scope in Heck arylation reaction of phenylboronic acids with olefins.a Supporting Information Supporting Information File 292: General procedure for Heck reactions, preparation of complex 6

Coupling of C-nitro-NH-azoles with arylboronic acids. A route to N-aryl-C-nitroazoles

• Marta K. Kurpet,
• Aleksandra Dąbrowska,
• Małgorzata M. Jarosz,
• Katarzyna Kajewska-Kania,
• Nikodem Kuźnik and
• Jerzy W. Suwiński

Beilstein J. Org. Chem. 2013, 9, 1517–1525, doi:10.3762/bjoc.9.173

• . The presence of the nitro group (a strong electron-withdrawing substituent) in the azole entails the adjustment of the conditions of N-arylation reaction. Besides a very recently published approach involving N-arylation of nitroazoles with diaryliodonium salts [20], already described methods utilize

Photoinduced synthesis of unsymmetrical diaryl selenides from triarylbismuthines and diaryl diselenides

• Yohsuke Kobiki,
• Shin-ichi Kawaguchi,
• Takashi Ohe and
• Akiya Ogawa

Beilstein J. Org. Chem. 2013, 9, 1141–1147, doi:10.3762/bjoc.9.127

• gel chromatography (the yield was determined by HPLC). Next, optimization of the reaction conditions was investigated as shown in Table 1. Irradiation by a tungsten lamp instead of a xenon lamp did not induce the desired arylation reaction (Table 1, entry 2), and in the dark, the reaction did not

Synthesis of phenanthridines via palladium-catalyzed picolinamide-directed sequential C–H functionalization

• Ryan Pearson,
• Shuyu Zhang,
• Gang He,
• Nicola Edwards and
• Gong Chen

Beilstein J. Org. Chem. 2013, 9, 891–899, doi:10.3762/bjoc.9.102

• , the arylation yield dropped significantly when the reaction was performed in toluene solvent at 120 °C (Table 1, entry 2). Addition of PivOH (0.3 equiv) gave little improvement (Table 1, entries 3 and 4). To our delight, the desired arylation reaction was largely restored with the application of 2

• important for the regioselectivity of the arylation reaction. For instance, the less hindered ortho position is preferentially arylated (e.g., 14) when a meta substitutent is present on the benzylpicolinamide. Aryl bromides are much less reactive compared with aryl iodide substrates 4. This is in accordance

• from easily accessible benzylamine picolinamides and aryl iodides. In the first step, an improved protocol allows us to carry out the Pd-catalyzed PA-directed C–H arylation reaction without the use of expensive silver additives. In the second step, application of PhI(OAc)2 and Cu(OAc)2 oxidant under

Recent advances in transition-metal-catalyzed intermolecular carbomagnesiation and carbozincation

• Kei Murakami and
• Hideki Yorimitsu

Beilstein J. Org. Chem. 2013, 9, 278–302, doi:10.3762/bjoc.9.34

• copper-catalyzed reaction of cyclopropene 3a with methylmagnesium reagent to afford 3b with perfect stereoselectivity (Scheme 19) [84]. Not only methylmagnesium reagents but also vinyl- or alkynylmagnesium reagents could be employed. Although the arylation reaction did not proceed under the same

Copper-catalyzed CuAAC/intramolecular C–H arylation sequence: Synthesis of annulated 1,2,3-triazoles

• Rajkumar Jeyachandran,
• Harish Kumar Potukuchi and
• Lutz Ackermann

Beilstein J. Org. Chem. 2012, 8, 1771–1777, doi:10.3762/bjoc.8.202

• fully substituted 1,2,3-triazoles with excellent chemo- and regioselectivities. Likewise, the optimized catalytic system proved applicable to the direct preparation of 1,2-diarylated azoles through a one-pot C–H/N–H arylation reaction. Keywords: cascade reaction; C–H functionalization; copper

Double N-arylation reaction of polyhalogenated 4,4’-bipyridines. Expedious synthesis of functionalized 2,7-diazacarbazoles

• Mohamed Abboud,
• Emmanuel Aubert and
• Victor Mamane

Beilstein J. Org. Chem. 2012, 8, 253–258, doi:10.3762/bjoc.8.26

• Nancy Université, BP 70239, Bd des Aiguillettes, 54506 Vandoeuvre-les-Nancy, France 10.3762/bjoc.8.26 Abstract Unusual 2,7-diazacarbazoles were prepared in one step from readily available tetra-halogenated 4,4’-bipyridines by using a double N-arylation reaction in the presence of the Pd–XPhos catalyst

• yield of 61% achieved with XPhos [38]. The bulk of the phosphine ligand enhances the stability and the activity of the catalytic system [39] thus allowing the use of an elevated temperature (120 °C) necessary for the double N-arylation reaction [20]. Encouraged by these results, we further explored the

Efficient synthesis of 1,3-diaryl-4-halo-1H-pyrazoles from 3-arylsydnones and 2-aryl-1,1-dihalo-1-alkenes

• Yiwen Yang,
• Chunxiang Kuang,
• Hui Jin,
• Qing Yang and
• Zhongkui Zhang

Beilstein J. Org. Chem. 2011, 7, 1656–1662, doi:10.3762/bjoc.7.195

• elimination of a hydrogen halide from 2-aryl-1,1-dihalo-1-alkenes 2 with Cs2CO3 as a base [36]. Then, haloalkyne reacts with 3-arylsydnone 1 in a 1,3-dipolar cycloaddition reaction. Finally, CO2 is lost [18][34] and pyrazole 3 is generated. Subsequently, the arylation reaction of pyrazoles 3 with iodobenzene

Synthesis of fluoranthenes by hydroarylation of alkynes catalyzed by gold(I) or gallium trichloride

• Sergio Pascual,
• Christophe Bour,
• Paula de Mendoza and
• Antonio M. Echavarren

Beilstein J. Org. Chem. 2011, 7, 1520–1525, doi:10.3762/bjoc.7.178

• synthesis of large polyarenes [40][41][42][43], which are related to the fullerenes [44], we used the palladium-catalyzed arylation reaction as the main tool [45][46][47][48]. We decided to try the triple hydroarylation of substrates of type 1 to give 3,9,15-triaryldiacenaphtho[1,2-j:1',2'-l]fluoranthenes 2

• with high efficiency in a one-pot transformation. The reaction is totally compatible with aryl bromides, which do not undergo subsequent arylation reaction due to the inertness of gold(I) catalysts towards oxidative addition reactions under homogeneous conditions [63][64]. Cationic gold complexes 5 and

C-Arylation reactions catalyzed by CuO-nanoparticles under ligand free conditions

• Mazaahir Kidwai,
• Saurav Bhardwaj and
• Roona Poddar

Beilstein J. Org. Chem. 2010, 6, No. 35, doi:10.3762/bjoc.6.35

• . Synthesis of 3-phenylpentane-2,4-dione using CuO-nanoparticles. Synthesis of diethyl 2-aryl-malonate using CuO-nanoparticles. C-arylation reaction catalyzed by different Cu catalystsa. CuO-nanoparticles catalyzed coupling reaction of acetylacetone and iodobenzene in various solventsa. C-arylation of

Continuous flow enantioselective arylation of aldehydes with ArZnEt using triarylboroxins as the ultimate source of aryl groups

• Julien Rolland,
• Xacobe C. Cambeiro,
• Carles Rodríguez-Escrich and
• Miquel A. Pericàs

Beilstein J. Org. Chem. 2009, 5, No. 56, doi:10.3762/bjoc.5.56

• obtained in slightly lower yield and enantioselectivity (entry 1, Table 1). This is probably due to the fact that the triethylboroxin co-product can trigger a non-enantioselective pathway for the arylation reaction; in fact, a decrease in the amount of (PhBO)3, as well as an increase in the amount of ZnEt2

• difficulty comes from the Bolm laboratory and has been based on the use of the comparatively less reactive mixed species PhEtZn, easily prepared from a mixture of Ph2Zn and Et2Zn [10][11][12][13]. With this strategy, it has become possible to achieve good levels of enantioselectivity in the arylation

• reaction, although usually at the cost of low catalytic activity, high catalytic loadings being required for the achievement of satisfactory yields [14][15]. In contrast, β-amino alcohol 1 (Figure 2), developed in our laboratory [16], showed high activity and enantioselectivity in the ethylation [16