Direct arylation catalysis with chloro[8-(dimesitylboryl)quinoline-κN]copper(I)

• Sem Raj Tamang and
• James D. Hoefelmeyer

Beilstein J. Org. Chem. 2016, 12, 2757–2762, doi:10.3762/bjoc.12.272

• literature. Coordination of Cu(I) with the ambiphilic ligand 1 to form the catalyst 2. Proposed mechanism of direct arylation catalyzed by 2 (X = Cl/I; Ar = aryl). Coupling reaction of aryl halides with benzene. Reactions were carried out with 4 mL of benzene and 0.4 mL of DMF. Supporting Information

High performance p-type molecular electron donors for OPV applications via alkylthiophene catenation chromophore extension

• Paul B. Geraghty,
• Calvin Lee,
• Jegadesan Subbiah,
• Wallace W. H. Wong,
• James L. Banal,
• Mohammed A. Jameel,
• Trevor A. Smith and
• David J. Jones

Beilstein J. Org. Chem. 2016, 12, 2298–2314, doi:10.3762/bjoc.12.223

• -bromothiophene-2-carboxaldehyde to generate the bithiophene 4, Scheme 3. It has previously been reported that direct coupling of 2-(trimethylsilyl)thiophene with aryl halides proceeds in good yield with protodesilylation being the major side reaction under the reaction conditions, even at short reaction times

Regiocontroled Pd-catalysed C5-arylation of 3-substituted thiophene derivatives using a bromo-substituent as blocking group

• Mariem Brahim,
• Hamed Ben Ammar,
• Jean-François Soulé and
• Henri Doucet

Beilstein J. Org. Chem. 2016, 12, 2197–2203, doi:10.3762/bjoc.12.210

• reactions can be performed, an organometallic compound must be synthesized. In 1990, Ohta and co-workers described the Pd-catalysed direct arylation of thiophene derivatives by coupling reaction with aryl halides [15][16]. This is a highly powerful method for a greener access to a very broad range of

Copper-catalyzed [3 + 2] cycloaddition of (phenylethynyl)di-p-tolylstibane with organic azides

• Mizuki Yamada,
• Mio Matsumura,
• Yuki Uchida,
• Masatoshi Kawahata,
• Yuki Murata,
• Naoki Kakusawa,
• Kentaro Yamaguchi and
• Shuji Yasuike

Beilstein J. Org. Chem. 2016, 12, 1309–1313, doi:10.3762/bjoc.12.123

• organoantimony compounds in organic synthesis has attracted much interest during the last two decades [25][26]. Trivalent organoantimony compounds (stibanes) such as aryl- and ethynylstibanes are useful transmetalation agents in Pd-catalyzed cross-coupling reactions with aryl halides and acyl chlorides [27][28

Stereoselective synthesis of tricyclic compounds by intramolecular palladium-catalyzed addition of aryl iodides to carbonyl groups

• Jakub Saadi,
• Christoph Bentz,
• Kai Redies,
• Dieter Lentz,
• Reinhold Zimmer and
• Hans-Ulrich Reissig

Beilstein J. Org. Chem. 2016, 12, 1236–1242, doi:10.3762/bjoc.12.118

• forming reactions of aryl halides that involve an insertion of the intermediate aryl palladium species into a carbonyl group are relatively rare (see discussion below). Therefore this serendipitous discovery led us to investigate the reaction in more detail. Results The required γ-ketoesters A bearing the

Cationic Pd(II)-catalyzed C–H activation/cross-coupling reactions at room temperature: synthetic and mechanistic studies

• Takashi Nishikata,
• Alexander R. Abela,
• Shenlin Huang and
• Bruce H. Lipshutz

Beilstein J. Org. Chem. 2016, 12, 1040–1064, doi:10.3762/bjoc.12.99

• yet to be conclusively demonstrated from the oxidative addition of anilide-derived, divalent palladacycles into aryl halides, although formation of octahedral Pd(IV) complexes from N-substituted biphenyl palladacycles that possess similar highly planar structures as found in the urea-derived

A convenient route to symmetrically and unsymmetrically substituted 3,5-diaryl-2,4,6-trimethylpyridines via Suzuki–Miyaura cross-coupling reaction

• Dariusz Błachut,
• Joanna Szawkało and
• Zbigniew Czarnocki

Beilstein J. Org. Chem. 2016, 12, 835–845, doi:10.3762/bjoc.12.82

• moiety is of crucial importance. As it was shown by Shen [47], Fu [48][49] and Monteith [50], the use of bulk and strongly electron-donating ligands (i.e., P(Cy)3 or P(t-Bu)3) accelerated the rate of the oxidative addition of aryl halides to the Pd-complex centre promoting the ligands dissociation

Iridium/N-heterocyclic carbene-catalyzed C–H borylation of arenes by diisopropylaminoborane

• Mamoru Tobisu,
• Takuya Igarashi and
• Naoto Chatani

Beilstein J. Org. Chem. 2016, 12, 654–661, doi:10.3762/bjoc.12.65

• derivatives by treatment with protecting groups in a one-pot reaction sequence. The reactivity of 1g has previously been well-exploited in catalytic borylation of aryl halides [22][23][24][25][26][27]. Herein, we report the C–H borylation of arenes using 1g catalyzed by an Ir/N-heterocyclic carbene (NHC

Carbon–carbon bond cleavage for Cu-mediated aromatic trifluoromethylations and pentafluoroethylations

• Tsuyuka Sugiishi,
• Hideki Amii,
• Kohsuke Aikawa and
• Koichi Mikami

Beilstein J. Org. Chem. 2015, 11, 2661–2670, doi:10.3762/bjoc.11.286

• − source and [CF3Cu] species with CuI are generated in situ. In the presence of CuI, CF3CO2Na undergoes trifluoromethylation with aryl halides via decarboxylation [33][34] (Scheme 1). A pentafluoroethyl group (C2F5) was fixed at the arene with sodium pentafluoropropionate [35] (Scheme 2). The reaction

• the decarboxylative trifluoromethylation of aryl halides [37] (Scheme 4). Not only iodobenzene but also 4-bromotoluene was trifluoromethylated by the [(NHC)Cu(TFA)] complex. The perfluoroalkylation reactions mentioned above require a stoichiometric amount of copper reagent, whereas it was found that

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

• ][8][9][10][11][12][13]. Despite the progress in recent years, the research on asymmetric coupling reactions is still relatively rare. In this review, we highlight the developments in copper-catalyzed asymmetric coupling reactions, including the asymmetric coupling of aryl halides with nucleophiles

• for the formation of carbon–carbon and carbon–heteroatom bonds as well as the asymmetric allylic substitution with a wide range of nucleophiles for the formation of C–C and carbon–heteroatom bonds. Review Copper-catalyzed coupling of aryl halides with nucleophiles Chiral auxiliary-induced aryl C–C

• -dimethylbutyrate. In this reaction, only one diastereoisomer was formed during the Ullmann coupling and the auxiliary is easily prepared and removed by hydrolysis after the coupling reaction (Scheme 3). In 2007, Breit et al. [22] employed a chiral tether to link two aryl halides for the enantioselective synthesis

Comparison of the catalytic activity for the Suzuki–Miyaura reaction of (η⁵-Cp)Pd(IPr)Cl with (η³-cinnamyl)Pd(IPr)(Cl) and (η³-1-t-Bu-indenyl)Pd(IPr)(Cl)

• Patrick R. Melvin,
• Nilay Hazari,
• Hannah M. C. Lant,
• Ian L. Peczak and
• Hemali P. Shah

Beilstein J. Org. Chem. 2015, 11, 2476–2486, doi:10.3762/bjoc.11.269

• ; homogeneous catalysis; NHC ligands; palladium; Suzuki–Miyaura reaction; Introduction The Suzuki–Miyaura reaction is a powerful synthetic method for forming C–C bonds between aryl halides or pseudo halides and organoborane containing species [1][2][3][4][5]. The most active catalysts are generally based on Pd

Copper-catalyzed arylation of alkyl halides with arylaluminum reagents

• Bijay Shrestha and
• Ramesh Giri

Beilstein J. Org. Chem. 2015, 11, 2400–2407, doi:10.3762/bjoc.11.261

• conditions, a catalyst derived from the combination of CuI and 2-(diphenylphosphino)-N,N-dimethylaniline (PN-1) remains highly effective for coupling many of these organometallic reagents with aryl halides. In order to expand the scope of our coupling reactions, we utilized the standard condtions for the

Cu(I)-catalyzed N,N’-diarylation of natural diamines and polyamines with aryl iodides

• Svetlana P. Panchenko,
• Alexei D. Averin,
• Maksim V. Anokhin,
• Olga A. Maloshitskaya and
• Irina P. Beletskaya

Beilstein J. Org. Chem. 2015, 11, 2297–2305, doi:10.3762/bjoc.11.250

• substantially enhance the yields in the reactions even with less reactive aryl halides. Cu(I)-catalyzed amination of ortho-disubstituted benzenes is a challenging task as earlier we demonstrated very low reactivity of 2-iodotoluene and 1,2-diiodobenzene [31]. Contrary to this, Pd(0)-catalyzed amination of 2

C–H bond halogenation catalyzed or mediated by copper: an overview

• Wenyan Hao and
• Yunyun Liu

Beilstein J. Org. Chem. 2015, 11, 2132–2144, doi:10.3762/bjoc.11.230

• catalysis in modern organic synthesis, herein, we would like to highlight the recent progress in the C–H bond halogenation with copper catalysis or mediation. Review Copper-catalyzed/mediated halogenation of the C(sp2)–H bond Halogenation of the arene C(sp2)–H bond In the synthesis of aryl halides employing

Efficient synthesis of π-conjugated molecules incorporating fluorinated phenylene units through palladium-catalyzed iterative C(sp²)–H bond arylations

• Fatiha Abdelmalek,
• Fazia Derridj,
• Safia Djebbar,
• Jean-François Soulé and
• Henri Doucet

Beilstein J. Org. Chem. 2015, 11, 2012–2020, doi:10.3762/bjoc.11.218

• arylated in β-position instead of α-position with the classical procedure employing aryl halides as coupling partners [53][55] and benzofuran regioselectively led to C2 arylated compounds instead of the mixtures of C2 and C3 arylated products obtained with aryl bromides [56]. Moreover, these processes are

• chlorides as coupling partners allowed the formation of heteroarylated polyfluorobenzenes. Then, in a second and third step, the PdCl(C3H5)(dppb)-catalyzed regioselective arylations using aryl halides as coupling partners furnished the desired triads or tetrads. Results and Discussion We started our

• direct arylation with aryl halides [62][63][64]. A similar reactivity trend was observed using 2-(2,3,4-trifluorophenyl)benzofuran (2) as starting material, which furnished the C3-arylated 2-(2,3,4-trifluorophenyl)benzofuran 10 in 58% yield with 92% regioselectivity. (Hetero)aryl triads containing a

Pyridine-promoted dediazoniation of aryldiazonium tetrafluoroborates: Application to the synthesis of SF₅-substituted phenylboronic esters and iodobenzenes

• George Iakobson,
• Junyi Du,
• Alexandra M. Z. Slawin and
• Petr Beier

Beilstein J. Org. Chem. 2015, 11, 1494–1502, doi:10.3762/bjoc.11.162

• compounds are accessed mainly by the reactions of arylmagnesium or aryllithium species with trialkylboronates [43][44], Pd- or Cu-catalyzed borylations of aryl halides using B2pin2, H-Bpin [45][46][47][48][49][50] or R2N-BH2 [51], direct borylations via aromatic C–H bond activations [52][53][54][55][56][57

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

• be employed after deproto-zincation (interception with aldehydes, phenyl disulfide and allyl bromide, or palladium-catalyzed cross-coupling with aryl halides) [35], we chose the iodolysis, which is the most efficient quench. In addition, it offers the possibility of a subsequent functionalization of

Reactions of nitroxides 15. Cinnamates bearing a nitroxyl moiety synthesized using a Mizoroki–Heck cross-coupling reaction

• Jerzy Zakrzewski and
• Bogumiła Huras

Beilstein J. Org. Chem. 2015, 11, 1155–1162, doi:10.3762/bjoc.11.130

• been obtained using the Mizoroki–Heck cross-coupling reaction between aryl halides and an olefin [7][13][14][15][16][17]. Because cinnamates themselves are also olefins, they can serve as cinnamic substrates to synthesize more complex cinnamates [18][19]. Cinnamic acid derivatives are also formed when

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

• to the N-arylation of MPTTFs and BPTTFs using a variety of aryl halides. Keywords: heterocycles; protecting groups; sulfur chemistry; tetrathiafulvalene; Ullman coupling; Introduction Tetrathiafulvalene (TTF) derivatives are of considerable interest in the fields of supramolecular chemistry and

• amidation of aryl halides [51][52]. Examples of TTF derivatives synthesised using this protocol by other groups include: MPTTF and BPTTF-triarylamine conjugates (as possible charge-transport materials) [53], MPTTF-triarylborane conjugates (with possible applications as fluoride sensors) [54], and MPTTF

• products (4c’, 4d’, 4f’ and 4g’) and a range of aryl halides is then possible. In this study we have investigated several p-substituted species (23-X–28-X, Scheme 6). As satisfactory results have been reported for similar arylations [29][53][54] when (±)-trans-1,2-diaminocyclohexane, 29 (Scheme 6), is used

Weakly nucleophilic potassium aryltrifluoroborates in palladium-catalyzed Suzuki–Miyaura reactions: relative reactivity of K[4-RC₆F₄BF₃] and the role of silver-assistance in acceleration of transmetallation

• Vadim V. Bardin,
• Anton Yu. Shabalin and
• Nicolay Yu. Adonin

Beilstein J. Org. Chem. 2015, 11, 608–616, doi:10.3762/bjoc.11.68

• reported by Kishi et al. [16] for the cross-coupling of alkenylboronic acids with alkenyl iodides in the presence of Ag2O and elucidated by formation of AgOH which acts like aqueous KOH or TlOH. Korenaga et al. [20] have studied Pd-catalyzed cross-coupling of C6F5B(OH)2 with aryl halides in the presence of

Palladium-catalyzed 2,5-diheteroarylation of 2,5-dibromothiophene derivatives

• Fatma Belkessam,
• Aidene Mohand,
• Jean-François Soulé,
• Abdelhamid Elias and
• Henri Doucet

Beilstein J. Org. Chem. 2014, 10, 2912–2919, doi:10.3762/bjoc.10.309

• -diheteroarylated thiophenes bearing two different heteroaryl units. Keywords: aryl halides; catalysis; C–H bond activation; direct arylation; heteroarenes; palladium; Introduction 2,2':5',2"-Terthiophene (or 2,5-di(2-thienyl)thiophene) (Figure 1) and many of its derivatives are important structures due to their

• ][9][10][11][12][13][14][15][16]. However, an organometallic derivative must be prepared to perform such reactions. In 1990, Ohta and co-workers reported the Pd-catalyzed direct arylation of heteroaromatics using aryl halides as coupling partners via a C–H bond activation [17][18]. Since then Pd

• -catalyzed direct arylation of heteroaryls, especially with aryl halides as coupling partners, has been shown to be a very powerful method for an easier and greener access to a very broad range of arylated heterocycles [19][20][21][22][23][24][25][26][27][28][29][30][31][32]. This method is more attractive

Copper-promoted hydration and annulation of 2-fluorophenylacetylene derivatives: from alkynes to benzo[b]furans and benzo[b]thiophenes

• Yibiao Li,
• Liang Cheng,
• Xiaohang Liu,
• Bin Li and
• Ning Sun

Beilstein J. Org. Chem. 2014, 10, 2886–2891, doi:10.3762/bjoc.10.305

• metal-free process for the synthesis of benzo[b]furans from 2-fluorophenylacetylene derivatives. But the reaction requires conditions with a high reaction temperature for satisfactory yields. Unfortunately, only benzo[b]furans were obtained in this reaction [30]. Typically, the aryl halides used in the

A novel 4-aminoantipyrine-Pd(II) complex catalyzes Suzuki–Miyaura cross-coupling reactions of aryl halides

• Claudia A. Contreras-Celedón,
• Darío Mendoza-Rayo,
• José A. Rincón-Medina and
• Luis Chacón-García

Beilstein J. Org. Chem. 2014, 10, 2821–2826, doi:10.3762/bjoc.10.299

• ]. The palladium-catalyzed cross-coupling of arylboronic acid and aryl halides in the Suzuki–Miyaura (SM) reaction is one of the most popular and important methods to obtain biaryls, which are essential structures of many important compounds such as natural products [7], agrochemicals [8

• , we report the synthesis of the new 4-aminoantipyrine–Pd(II) complex [4-AAP–Pd(II)] by mixing Li2PdCl4, 4-aminoantipyrine in presence of NaOAc in MeOH at room temperature, and its performance as catalysts in SM cross-coupling reaction of structurally different aryl halides with phenylboronic acids

• organic reactions. Synthesis of 4-aminoantipyrine-Pd(II) complex. Reaction of different aryl halides with substituted arylboronic acids. Reaction conditions: phenylboronic acid (0.40 mmol), aryl halide (0.27 mmol), 4-AAP–Pd(II) (0.3 mol %), 2 M K2CO3 (0.67 mmol), ethanol (2 mL), heating under reflux for 4

A simple copper-catalyzed two-step one-pot synthesis of indolo[1,2-a]quinazoline

• Chunpu Li,
• Lei Zhang,
• Shuangjie Shu and
• Hong Liu

Beilstein J. Org. Chem. 2014, 10, 2441–2447, doi:10.3762/bjoc.10.254

• aryl halides with active methylene compounds such as ethyl acetoacetate, malononitrile, cyanoacetate and their equivalents [8][9][10][11][12][13][14][15]. Copper-catalyzed domino reactions have also been used in the synthesis of nitrogen-containing compounds [16][17][18][19][20]. Ma et al reported a

Exploration of C–H and N–H-bond functionalization towards 1-(1,2-diarylindol-3-yl)tetrahydroisoquinolines

• Michael Ghobrial,
• Marko D. Mihovilovic and
• Michael Schnürch

Beilstein J. Org. Chem. 2014, 10, 2186–2199, doi:10.3762/bjoc.10.226

• completion, it could be demonstrated that most of the excess could be re-isolated (2.14 equiv of 4-iodoanisole were recovered) after column chromatography which is important in cases where expensive aryl halides are employed. Overall it could be demonstrated that 1-(1,2-diarylindol-3-yl)-N-PG-THIQs 1 can be