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

• featuring an ambiphilic ligand, (quinolin-8-yl)dimesitylborane. Direct arylation could be achieved with 0.2 mol % catalyst and 3 equivalents of base (KO(t-Bu)) at 80 °C to afford TON ≈160–190 over 40 hours. Keywords: catalysis; C–C coupling; C–H activation; copper; direct arylation; Introduction Coupling

• ]. Recently, we reported the Pd(II) complex catalyzed Heck-type C–C coupling [51]. The observation may implicate reductive elimination and oxidative addition can cycle repeatedly on the palladium center coordinated to 1. With this in mind, we sought to utilize the Cu(I) complex, chloro[8-(dimesitylboryl

Electron-transfer-initiated benzoin- and Stetter-like reactions in packed-bed reactors for process intensification

• Anna Zaghi,
• Daniele Ragno,
• Graziano Di Carmine,
• Carmela De Risi,
• Olga Bortolini,
• Pier Paolo Giovannini,
• Giancarlo Fantin and
• Alessandro Massi

Beilstein J. Org. Chem. 2016, 12, 2719–2730, doi:10.3762/bjoc.12.268

• ). Keywords: C–C coupling; continuos-flow; diketone; electron-transfer; umpolung; Introduction The polarity reversal (umpolung) of carbonyl compounds by N-heterocyclic carbene (NHC) or cyanide catalysis represents a straightforward strategy for the synthesis of valuable molecules such as, among the many

The direct oxidative diene cyclization and related reactions in natural product synthesis

• Juliane Adrian,
• Leona J. Gross and
• Christian B. W. Stark

Beilstein J. Org. Chem. 2016, 12, 2104–2123, doi:10.3762/bjoc.12.200

• . Venustatriol (96) could then be obtained by C–C-coupling with the corresponding THP fragment in an enantioselective fashion. Glaciapyrrol A Glaciapyrrol A (100), B and C form a family of pyrrolo sesquiterpenoids which have been isolated in 2005 from a marine Streptomyces sp. (NPS008187) by Macherla et al. [161

Thiophene-forming one-pot synthesis of three thienyl-bridged oligophenothiazines and their electronic properties

• Dominik Urselmann,
• Konstantin Deilhof,
• Bernhard Mayer and
• Thomas J. J. Müller

Beilstein J. Org. Chem. 2016, 12, 2055–2064, doi:10.3762/bjoc.12.194

• oligophenothiazines. TD-DFT and even semiempirical ZINDO calculations reproduce the trends of longest wavelengths absorption bands and allow the assignment of these transitions to possess largely charge-transfer character from the adjacent phenothiazinyl moieties to the central thienyl unit. Keywords: C–C coupling

Hydroxy-functionalized hyper-cross-linked ultra-microporous organic polymers for selective CO₂ capture at room temperature

• Partha Samanta,
• Priyanshu Chandra and
• Sujit K. Ghosh

Beilstein J. Org. Chem. 2016, 12, 1981–1986, doi:10.3762/bjoc.12.185

• two hydroxy-functionalised hyper-cross-linked microporous organic polymers for selective CO2 capture at room temperature. Both compounds (HCP-91 and HCP-94) were synthesized via hyper-cross-linked C–C coupling of hydroxyl-functionalised aromatic rings by using a Friedel–Craftys reaction. At different

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

• related trans-compound 8 (11%) together with the de-iodinated product 9 (25%) and the indane derivative 10 as major component (62%). The C–C coupling reaction to 8 seems to be hindered in this case, probably due to the steric bulk of the isopropyl group. The formation of indane derivative 10 occurs by an

Biradical vs singlet oxygen photogeneration in suprofen–cholesterol systems

• Fabrizio Palumbo,
• Francisco Bosca,
• Isabel M. Morera,
• Inmaculada Andreu and
• Miguel A. Miranda

Beilstein J. Org. Chem. 2016, 12, 1196–1202, doi:10.3762/bjoc.12.115

• photoproducts 4 and 5, respectively. By contrast, under the same conditions, 3 did not give rise to any isolable Ch-derived product. These results point to an intramolecular hydrogen abstraction in 1 and 2 from the C7 position of Ch and subsequent C–C coupling of the generated biradicals. Interestingly, 2 was

• two active moieties. The nature of the photoproducts formed from 1 and 2 point to an intramolecular HA from the C7 position of Ch and subsequent C–C coupling of the generated biradicals. The structures of compounds 4 and 5 were unambiguously assigned on the basis of their NMR spectroscopic data (1H

Catalytic asymmetric synthesis of biologically important 3-hydroxyoxindoles: an update

• Bin Yu,
• Hui Xing,
• De-Quan Yu and
• Hong-Min Liu

Beilstein J. Org. Chem. 2016, 12, 1000–1039, doi:10.3762/bjoc.12.98

• values. In addition, aliphatic β-ketoacids can also be used in the reaction, giving the corresponding alkylated 3-hydroxyoxindoles in good results under the optimized conditions. Krische and co-workers reported the first Ru-catalyzed hydrohydroxyalkylation of unactivated olefins. The direct C–C coupling

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

• loading. Based on our accrued experience [52], in a first attempt, we employed Cu(OTf)2 (10 mol %) in refluxing 1,2-dichlorethane (DCE) to effect C–C coupling, but the reaction provided (phenoxymethylene)dibenzene (12) as the only product formed through the C–O coupling (Chan–Lam–Evans coupling product

• triarylmethane 11s was found to be unstable when kept as a solution in hexane. However, the compound was stable as a solid for at least two months when refrigerated (+5 °C). To demonstrate an application of our newly developed Cu(OTf)2-catalyzed C–C coupling reaction for the synthesis of triarylmethanes, we

Versatile deprotonated NHC: C,N-bridged dinuclear iridium and rhodium complexes

• Albert Poater

Beilstein J. Org. Chem. 2016, 12, 117–124, doi:10.3762/bjoc.12.13

• effective for any catalytic reaction, but some successful applications were achieved in the field of Ru-catalyzed metathesis of olefins [9][10][11][12], Ir-catalyzed hydrogenation [13][14], Pd-catalyzed C=C coupling reactions [15][16], Ir-catalyzed CO2 fixation [17][18], and/or functionalization of alkenes

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

• 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

• coupling The biaryl motif is a key subunit in many natural products and axially chiral ligands. The classical Ullmann coupling is one of the most important methods for the practical synthesis of biaryls [14]. However, only few reports of an asymmetric version of the Ullmann coupling have been documented

Versatile synthesis and biological evaluation of novel 3’-fluorinated purine nucleosides

• Hang Ren,
• Haoyun An,
• Paul J. Hatala,
• William C. Stevens Jr,
• Jingchao Tao and
• Baicheng He

Beilstein J. Org. Chem. 2015, 11, 2509–2520, doi:10.3762/bjoc.11.272

• , substituted pyridine boronic acids [52][53][54] were coupled with intermediate 26 using Method III in DME–water to provide the desired 6-aryl products 37–40 (entries 12–15, Table 1). These results indicated that the DME–water solvent system was more favourable for more challenging Suzuki C–C coupling

SmI₂-mediated dimerization of indolylbutenones and synthesis of the myxobacterial natural product indiacen B

• Nils Marsch,
• Peter G. Jones and
• Thomas Lindel

Beilstein J. Org. Chem. 2015, 11, 1700–1706, doi:10.3762/bjoc.11.184

• - or 4-iodinated indoles reported [16][17][18][19][20]. Having natural product 5 in hand, we wondered whether and which intra or intermolecular C–C coupling would occur under reductive conditions and whether or not such a reaction could run without participation of the indole enamine moiety. After

Selected synthetic strategies to cyclophanes

• Sambasivarao Kotha,
• Mukesh E. Shirbhate and
• Gopalkrushna T. Waghule

Beilstein J. Org. Chem. 2015, 11, 1274–1331, doi:10.3762/bjoc.11.142

Highly selective palladium–benzothiazole carbene-catalyzed allylation of active methylene compounds under neutral conditions

• Antonio Monopoli,
• Pietro Cotugno,
• Carlo G. Zambonin,
• Francesco Ciminale and
• Angelo Nacci

Beilstein J. Org. Chem. 2015, 11, 994–999, doi:10.3762/bjoc.11.111

• allylic alkylation of nucleophiles [30][31][32][33][34][35][36]. Some years ago, we synthesized the first example of Pd–benzothiazol-2-ylidene complex I (Figure 1), which proved to be an efficient catalyst for several C–C coupling reactions (like carbonylations and Heck olefinations) carried out in both

Cross-dehydrogenative coupling for the intermolecular C–O bond formation

• Igor B. Krylov,
• Vera A. Vil’ and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2015, 11, 92–146, doi:10.3762/bjoc.11.13

• mechanisms of these processes. Among cross-dehydrogenative coupling reactions, C–C coupling reactions have been studied in most detail [1][2][3][4][5][6][7][8][9][10][11][12][13][14], whereas the C–O coupling is less well-known (Scheme 2). We present the first systematic review of the main approaches to the

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

• –Hartwig coupling; C–C coupling; C–H functionalization; iron catalysis; regioselective arylation; Introduction 1,2,3,4-Tetrahydroisoquinolines (THIQs) are common substructures in natural products [1]. The structural motif of 1-(indol-3-yl)-THIQ is also found in compounds with biological activity, for

Homogeneous and heterogeneous photoredox-catalyzed hydroxymethylation of ketones and keto esters: catalyst screening, chemoselectivity and dilution effects

• Axel G. Griesbeck and
• Melissa Reckenthäler

Beilstein J. Org. Chem. 2014, 10, 1143–1150, doi:10.3762/bjoc.10.114

• product without the need of sacrificial components. The latter process proceeds with a high degree of atom economy [16]. We have recently demonstrated this for the azido-hydroperoxidation of alkenes, a convenient method for the synthesis of 1,2-amino alcohols [17][18]. In the field of C–C coupling

Clean and fast cross-coupling of aryl halides in one-pot

• Valerica Pandarus,
• Geneviève Gingras,
• François Béland,
• Rosaria Ciriminna and
• Mario Pagliaro

Beilstein J. Org. Chem. 2014, 10, 897–901, doi:10.3762/bjoc.10.87

• sol–gel-entrapped SiliaCat DPP-Pd catalyst (Scheme 1) [10]: SiliaCat DPP-Pd is a commercially available catalyst [11] made of an organosilica matrix functionalized with diphenylphosphine ligands bound to Pd2+ (Figure 1). The catalyst, which is highly active in C–C coupling reactions [12], has typical

Rapid pseudo five-component synthesis of intensively blue luminescent 2,5-di(hetero)arylfurans via a Sonogashira–Glaser cyclization sequence

• Fabian Klukas,
• Alexander Grunwald,
• Franziska Menschel and
• Thomas J. J. Müller

Beilstein J. Org. Chem. 2014, 10, 672–679, doi:10.3762/bjoc.10.60

• interesting due to their bright blue luminescence with remarkably high quantum yields. The electronic structure of the title compounds is additionally studied with DFT computations. Keywords: C–C coupling; copper; DFT; fluorescence; furans; mircowave-assisted synthesis; multicomponent reactions; palladium

Synthesis and structure of trans-bis(1,4-dimesityl-3-methyl-1,2,3-triazol-5-ylidene)palladium(II) dichloride and diacetate. Suzuki–Miyaura coupling of polybromoarenes with high catalytic turnover efficiencies

• Jeelani Basha Shaik,
• Venkatachalam Ramkumar,
• Babu Varghese and
• Sethuraman Sankararaman

Beilstein J. Org. Chem. 2013, 9, 698–704, doi:10.3762/bjoc.9.79

• structures of the chloro (1) as well as the corresponding acetato (2) complexes are also reported and compared with the corresponding complexes of 1,4-diphenyl-3-methyl-1,2,3-triazol-5-ylidene as the ligand. Keywords: C–C coupling; N-heterocyclic carbene; palladium; Suzuki–Miyaura coupling; 1,2,3

• find application in the areas of molecular electronics, organic discotic liquid crystals and OLEDs [24][25]. One of the ways to approach the synthesis of these interesting compounds is to carry out multiple C–C coupling reactions with suitable polybromoarene derivatives. In multiple C–C coupling

Iron-containing mesoporous aluminosilicate catalyzed direct alkenylation of phenols: Facile synthesis of 1,1-diarylalkenes

• Satyajit Haldar and
• Subratanath Koner

Beilstein J. Org. Chem. 2013, 9, 49–55, doi:10.3762/bjoc.9.6

• reflux [28]. Further developments include the metal trifluoromethanesulfonate-catalyzed Friedel–Crafts alkenylation of arenes using alkynes by Tsuchimoto et al. [29] and the addition of simple arenes to arylacetylenes to afford exclusive 1,1-diarylethylenes through a C–C coupling reaction catalyzed by a

• at 80 °C, i.e., in cyclohexane under reflux. Since a number of pure aluminosilicates are known to catalyze C–C coupling reactions [34][35][36][37][38][39][40][41][42], a detailed investigation was performed with various available aluminosilicate and siliceous materials to understand the necessity of

• integrity was destroyed by proper treatment [48]. In that case, a long reaction time was observed (Table 2, entry 9), as in the case of HSZ-360-Y. On the basis of the optimized reaction conditions, the scope of this Fe-Al-MCM-41 catalyzed C–C coupling reaction was further investigated. Various substituted

The chemistry of bisallenes

• Henning Hopf and
• Georgios Markopoulos

Beilstein J. Org. Chem. 2012, 8, 1936–1998, doi:10.3762/bjoc.8.225

• ), but the composition of the product mixture is anything but simple (Scheme 5) [32][33][34][35][36]. Not only are the three isomeric C3-coupling products 38 to 40 produced, but also those of 37 with the Grignard reagent, 41 and 42 (R = Et, n-Pr). All of these C–C-coupling reactions are thought to occur

Syntheses and applications of furanyl-functionalised 2,2’:6’,2’’-terpyridines

• Jérôme Husson and
• Michael Knorr

Beilstein J. Org. Chem. 2012, 8, 379–389, doi:10.3762/bjoc.8.41

• literature example for this purpose uses the Stille reaction [33]. This C–C coupling, which involves the reaction between a halogenated or equivalent starting material and an organotin compound, was used to prepare 12 from 4′-(trifluoromethanesulfonyl)-2,2′′:6′,2′′-terpyridine (34) [34] and 2

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

• cycloaddition between 3-arylsydnones 1 and 2-aryl-1,1-dihalo-1-alkenes 2 (Scheme 1). 1,3-Diaryl-4-halo-1H-pyrazoles were found to be important intermediates that could easily be converted into 1,2,4-triaryl- or 1,2,5-triaryl-substituted pyrazoles via a Pd-catalyzed C–C coupling reaction. To the best of our