Synthesis of new p-tert-butylcalix[4]arene-based polyammonium triazolyl amphiphiles and their binding with nucleoside phosphates

• Vladimir A. Burilov,
• Guzaliya A. Fatikhova,
• Mariya N. Dokuchaeva,
• Ramil I. Nugmanov,
• Diana A. Mironova,
• Pavel V. Dorovatovskii,
• Victor N. Khrustalev,
• Svetlana E. Solovieva and
• Igor S. Antipin

Beilstein J. Org. Chem. 2018, 14, 1980–1993, doi:10.3762/bjoc.14.173

• /bjoc.14.173 Abstract The synthesis of new calix[4]arenes adopting a cone stereoisomeric form bearing two or four azide fragments on the upper rim and water-soluble triazolyl amphiphilic receptors with two or four polyammonium headgroups via copper-catalyzed azide–alkyne cycloaddition reaction has been

• solutions. Results and Discussion Synthesis of polyammonium calix[4]arene derivatives The functionalization of calix[4]arenes with azide groups paves the way to introduce a wide variety of functional groups [27] on the upper rim of the macrocycle by, e.g., the copper-catalyzed azide–alkyne cycloaddition

• adopted by calix[4]arenes containing non-bulky substituents at the upper rim [34]. Then, azido compounds 4a,b and 8a,b were subjected to copper-catalyzed reaction with 3-bis[2-(tert-butoxycarbonylamino)ethyl]propargylamine (Scheme 3). The syntheses were carried out for 4 hours at 40 °C in toluene and the

Synthesis and photophysical studies of a multivalent photoreactive Ru^II-calix[4]arene complex bearing RGD-containing cyclopentapeptides

• Sofia Kajouj,
• Lionel Marcelis,
• Alice Mattiuzzi,
• Adrien Grassin,
• Damien Dufour,
• Pierre Van Antwerpen,
• Didier Boturyn,
• Eric Defrancq,
• Mathieu Surin,
• Julien De Winter,
• Pascal Gerbaux,
• Ivan Jabin and
• Cécile Moucheron

Beilstein J. Org. Chem. 2018, 14, 1758–1768, doi:10.3762/bjoc.14.150

• anchoring i) of the photoreactive [Ru(TAP)2phen]2+ complex on the calix[4]arene small rim through a peptide-type coupling and ii) of the four c-[RGDfK] moieties on the opposite rim through a copper-catalyzed azide–alkyne cycloaddition (CuAAC) [66][67][68] (Figure 1). It was thus necessary to block the calix

• + CF3COO−]+ by comparison between the experimental and theoretical isotope distributions (see Supporting Information File 1). With RuII-calix[4]arene complex 7 in hands, we next moved to the introduction of the cellular targeting units on the large rim through copper-catalyzed azide–alkyne cycloaddition

Cobalt-catalyzed C–H cyanations: Insights into the reaction mechanism and the role of London dispersion

• Eric Detmar,
• Valentin Müller,
• Daniel Zell,
• Lutz Ackermann and
• Martin Breugst

Beilstein J. Org. Chem. 2018, 14, 1537–1545, doi:10.3762/bjoc.14.130

• comparison with previous computational investigations on copper-catalyzed ortho C–H cyanations of vinylarenes revealed that those reactions take place via a completely different mechanism involving two distinct catalytic cycles (copper-catalyzed electrophilic cyanative dearomatization and base-catalyzed

Hypervalent organoiodine compounds: from reagents to valuable building blocks in synthesis

• Gwendal Grelier,
• Benjamin Darses and
• Philippe Dauban

Beilstein J. Org. Chem. 2018, 14, 1508–1528, doi:10.3762/bjoc.14.128

• ]. The use of this acid as an oxygen nucleophile, then, has been more fully investigated by the groups of Szabó and Sodeoka who have simultaneously described the copper-catalyzed benzoyloxy-trifluoromethylation of alkenes and alkynes using Togni’s reagent 5. The group of Szabó has first reported the use

• -anti-addition are selectively isolated (Scheme 6) [39]. The proposed radical mechanism, which takes into account the beneficial effect of the bulky monophosphine P(t-Bu)3 on the reaction rate, is consistent with that reported by Szabó (Scheme 4b). The scope of the copper-catalyzed benzoyloxy

• heterocycles can also be obtained in good yields. The reaction is believed to involve either a tertiary radical intermediate or a carbocationic species, both being able to undergo a 5-exo-dig type cyclization to afford compounds 19. The copper-catalyzed benzoyloxy-trifluoromethylation has also been applied to

[3 + 2]-Cycloaddition reaction of sydnones with alkynes

• Veronika Hladíková,
• Jiří Váňa and
• Jiří Hanusek

Beilstein J. Org. Chem. 2018, 14, 1317–1348, doi:10.3762/bjoc.14.113

• mechanism). Copper-catalyzed reaction of sydnones with terminal alkynes A substantial breakthrough in the field of 3-arylsydnone-terminal alkyne cycloaddition was achieved by Taran’s group in 2013 [3]. They developed a regioselective Cu(I)-phenanthroline-catalyzed variant of this reaction (i.e., copper

• , in deuteric solvent hydrolyzed to give 3-deutero pyrazole. However, Fokin et al. has recently [123] revealed that monomeric copper acetylide complexes are not reactive toward organic azides in analogous copper-catalyzed alkyne–azide cycloaddition (CuAAC) and the catalysis by an external Cu(I) salt is

• niraparib. Reaction of sydnones with 1,3-/1,4-benzdiyne equivalents. Reaction of sydnones with heterocyclic strained cycloalkynes. Mono-copper catalyzed cycloaddition reaction. Di-copper catalyzed cycloaddition reaction. Thermal cycloaddition of sydnones with symmetrical non-cyclic alkynes. Bimolecular rate

Nanoreactors for green catalysis

• M. Teresa De Martino,
• Loai K. E. A. Abdelmohsen,
• Floris P. J. T. Rutjes and
• Jan C. M. van Hest

Beilstein J. Org. Chem. 2018, 14, 716–733, doi:10.3762/bjoc.14.61

• these Pd-catalytic micelles was also achieved while catalyzing reactions involving less reactive or sterically hindered species. Handa et al. described a self-assembled TPGS-750M micelle (shown in Scheme 1), that allowed for copper-catalyzed Suzuki–Myaura coupling of aryl iodides (Scheme 2) [70]. When

Cobalt-catalyzed directed C–H alkenylation of pivalophenone N–H imine with alkenyl phosphates

• Wengang Xu and
• Naohiko Yoshikai

Beilstein J. Org. Chem. 2018, 14, 709–715, doi:10.3762/bjoc.14.60

• alkenylation reaction, affording the product 3aj with an E/Z ratio of 4:1. In our previous study on the C–H alkylation and arylation of pivalophenone N–H imines, we demonstrated that the pivaloyl imine readily undergoes fragmentation into a cyano group via an iminyl radical under peroxide photolysis or copper

• -catalyzed aerobic conditions [29]. Under the same peroxide photolysis conditions (t-BuOOt-Bu with UV (254 nm) irradiation), the ortho-alkenylated imine 3aa underwent a C–N bond-forming cyclization to afford the spirocyclic imine 4 in 81% yield (Scheme 4). The reaction likely involves the initial formation

Diastereoselective auxiliary- and catalyst-controlled intramolecular aza-Michael reaction for the elaboration of enantioenriched 3-substituted isoindolinones. Application to the synthesis of a new pazinaclone analogue

• Romain Sallio,
• Stéphane Lebrun,
• Frédéric Capet,
• Francine Agbossou-Niedercorn,
• Christophe Michon and
• Eric Deniau

Beilstein J. Org. Chem. 2018, 14, 593–602, doi:10.3762/bjoc.14.46

• -receptor agonists [8][9][10][11][12][13][14][15][16]. Indeed, the copper-catalyzed N-arylation of (3S)-26 was performed in dioxane with N,N-dimethylethylenediamine as ligand [27] to deliver the targeted pazinaclone analogue (3S)-27 in a fair yield (66%) without significant loss in enantiomeric purity

Copper-catalyzed asymmetric methylation of fluoroalkylated pyruvates with dimethylzinc

• Kohsuke Aikawa,
• Kohei Yabuuchi,
• Kota Torii and
• Koichi Mikami

Beilstein J. Org. Chem. 2018, 14, 576–582, doi:10.3762/bjoc.14.44

• a catalytic amount of a chiral diphosphine, but without copper. Experimental Typical procedure for copper-catalyzed asymmetric methylation of fluoroalkylated pyruvates: To a mixture of CuTC (1.0 mg, 0.005 mmol) and (R)-BTFM-Garphos (5.7 mg, 0.0048 mmol) was added CH2Cl2 (1.0 mL) at room temperature

• determined by 19F NMR analysis using benzotrifluoride (BTF) as an internal standard. aReaction was carried out without CuTC. Copper-catalyzed asymmetric methylation. Optimization of reaction conditions. Supporting Information Supporting Information File 24: Experimental details and characterization data of

Synthesis and biological evaluation of RGD and isoDGR peptidomimetic-α-amanitin conjugates for tumor-targeting

• Lizeth Bodero,
• Paula López Rivas,
• Barbara Korsak,
• Torsten Hechler,
• Andreas Pahl,
• Christoph Müller,
• Daniela Arosio,
• Luca Pignataro,
• Cesare Gennari and
• Umberto Piarulli

Beilstein J. Org. Chem. 2018, 14, 407–415, doi:10.3762/bjoc.14.29

• disulfide linker in the cytoplasm. In another example, Perrin and co-workers conjugated the N-propargylasparagine of an amanitin analog to a cycloRGD integrin ligand (cyclo[RGDfK]) using a copper-catalyzed azide–alkyne cycloaddition [8]. The conjugates were tested in the U87 glioblastoma cell line, but only

Progress in copper-catalyzed trifluoromethylation

• Guan-bao Li,
• Chao Zhang,
• Chun Song and
• Yu-dao Ma

Beilstein J. Org. Chem. 2018, 14, 155–181, doi:10.3762/bjoc.14.11

• the trifluoromethyl group (CF3) in biologically active molecules promote the development of novel methods to construct C–CF3 bonds in the past few years. Among the many methods developed, copper-catalyzed trifluoromethylation has gained enormous interest due to its high efficiency and cheapness

• trifluoromethylation reagents. Review Copper-catalyzed trifluoromethylation of aryl and alkyl halides The first example of copper-promoted perfluoroalkylation of aromatic halides was presented in a US patent 1968 [9]. Since then, the copper-catalyzed trifluoromethylation of aromatic compounds has entered a stage of

• reported by the group of Li and Duan, with sodium trifluoroacetate as the trifluoromethyl source and using Ag2O as a promoter (Scheme 5) [17]. Subsequently, Beller and co-workers [18] finished a copper-catalyzed trifluoromethylation of aryl iodides with inexpensive methyl trifluoroacetate (MTFA) (Scheme 6

Synthetic mRNA capping

• Fabian Muttach,
• Nils Muthmann and
• Andrea Rentmeister

Beilstein J. Org. Chem. 2017, 13, 2819–2832, doi:10.3762/bjoc.13.274

• ) followed by treatment with aqueous ammonia (rt, 3 h). Click chemistry for the preparation of capped RNA and cap analogues. (A) Preparation of capped RNA via a copper-catalyzed azide–alkyne cycloaddition (CuAAC) of an azido-modified cap analogue with a 5'-alkyne bearing RNA [120]. (B) An alkyne-modified

Recent progress in the racemic and enantioselective synthesis of monofluoroalkene-based dipeptide isosteres

• Myriam Drouin and
• Jean-François Paquin

Beilstein J. Org. Chem. 2017, 13, 2637–2658, doi:10.3762/bjoc.13.262

• starting from the commercially available protected chiral hydroxyl ester 75. Reduction to the aldehyde followed by coupling with bromodifluoropropene gave two diastereoisomers 76a and 76b separable by flash chromatography. Then, the copper-catalyzed defluorinative allylic alkylation using Grignard reagents

• and co-workers. Synthesis of the tripeptide Boc-Asp(OBn)-Pro-ψ[(Z)-CF=CH)-Val-CH2OH by Miller and co-workers. Copper-catalyzed synthesis of monofluoralkenes by Taguchi and co-workers. One-pot intramolecular redox reaction to access amide-type isosteres by Otaka and co-workers. Copper-mediated

Solvent-free copper-catalyzed click chemistry for the synthesis of N-heterocyclic hybrids based on quinoline and 1,2,3-triazole

• Martina Tireli,
• Silvija Maračić,
• Stipe Lukin,
• Marina Juribašić Kulcsár,
• Dijana Žilić,
• Mario Cetina,
• Ivan Halasz,
• Silvana Raić-Malić and
• Krunoslav Užarević

Beilstein J. Org. Chem. 2017, 13, 2352–2363, doi:10.3762/bjoc.13.232

• Engineering and Technology, University of Zagreb, Marulićev trg 20, HR-10000 Zagreb, Croatia University of Zagreb, Faculty of Textile Technology, Department of Applied Chemistry, Prilaz baruna Filipovića 28a, HR-10000 Zagreb, Croatia 10.3762/bjoc.13.232 Abstract Copper-catalyzed mechanochemical click

• spin resonance (ESR) spectroscopy; in situ Raman monitoring; mechanochemistry; quinoline; solid-state click chemistry; Introduction The copper-catalyzed azide–alkyne cycloaddition (CuAAC) represents a prime example of click chemistry. Click chemistry describes “a set of near-perfect” reactions [1] for

Superstructures with cyclodextrins: Chemistry and applications IV

• Gerhard Wenz

Beilstein J. Org. Chem. 2017, 13, 2157–2159, doi:10.3762/bjoc.13.215

• was assembled from two monosubstituted α-CD rings, α,ω-dodecamethylene diazide axis, and two bulky alkyne stoppers through a copper-catalyzed [2 + 3] cycloaddition in one step. Because of the attached gadolinium complexes, this rotaxane showed a high NMR relaxivity, making it suitable as a probe for

Mechanochemical synthesis of small organic molecules

• Tapas Kumar Achar,
• Anima Bose and
• Prasenjit Mal

Beilstein J. Org. Chem. 2017, 13, 1907–1931, doi:10.3762/bjoc.13.186

• example of a double Sonogashira reaction is shown [60]. Oxidative cross-dehydrogenative coupling Copper-catalyzed mechanochemical oxidative cross-dehydrogenative coupling (CDC) reactions [61][62][63][64][65][66] of tetrahydroisoquinolines with alkynes and indoles was reported by Su and co-workers (Scheme

• ][75][76]. In view of this, chemists have introduced alternative energy sources like, microwave, sonication, mechanomilling, etc. [12][27][77]. Su and co-workers reported a copper-catalyzed arylation of anilines using arylboronic acid under high speed ball-milling conditions. Using 1.0 equiv of Cu(OAc

• ]. Mechanochemical Suzuki reaction [56]. Mechanochemical Suzuki–Miyaura coupling by LAG [57]. Mechanochemical Heck reaction [59]. a) Sonogashira coupling under milling conditions. b) The representative example of a double Sonogashira reaction of p-iodoacetophenone with 1,4-bis-ethynyl benzene. Copper-catalyzed CDC

Mechanochemical synthesis of thioureas, ureas and guanidines

• Vjekoslav Štrukil

Beilstein J. Org. Chem. 2017, 13, 1828–1849, doi:10.3762/bjoc.13.178

• chlorpropamide or the 2nd generation drugs like glibenclamide (Figure 1). These molecules were interesting synthetic targets for our mechanochemical approach which is based on a stoichiometric base-assisted or copper-catalyzed coupling of sulfonamides and iso(thio)cyanates [48]. For that purpose, 0.5–1 equiv of

The chemistry and biology of mycolactones

• Matthias Gehringer and
• Karl-Heinz Altmann

Beilstein J. Org. Chem. 2017, 13, 1596–1660, doi:10.3762/bjoc.13.159

Syntheses of 3,4- and 1,4-dihydroquinazolines from 2-aminobenzylamine

• Jimena E. Díaz,
• Silvia Ranieri,
• Nadia Gruber and
• Liliana R. Orelli

Beilstein J. Org. Chem. 2017, 13, 1470–1477, doi:10.3762/bjoc.13.145

• intramolecular conjugate addition to an α,β-unsaturated ester [12][13][14][15] or copper-catalyzed annulation of N-arylamidines [41], among others [42]. Most of the already mentioned methods have been applied to the synthesis of 3,4-dihydroquinazolines. Among them, only a few were used for the preparation of 1,4

BODIPY-based fluorescent liposomes with sesquiterpene lactone trilobolide

• Ludmila Škorpilová,
• Silvie Rimpelová,
• Michal Jurášek,
• Miloš Buděšínský,
• Jana Lokajová,
• Roman Effenberg,
• Petr Slepička,
• Tomáš Ruml,
• Eva Kmoníčková,
• Pavel B. Drašar and
• Zdeněk Wimmer

Beilstein J. Org. Chem. 2017, 13, 1316–1324, doi:10.3762/bjoc.13.128

• compound is shown in Scheme 1, part B. Propargyl-ChL [35] was introduced into Huisgen copper-catalyzed 1,3-dipolar cycloaddition [36] (CuAAC) with BODIPY 3. This microwave-assisted reaction catalyzed by CuSO4·5H2O, sodium ascorbate and a catalytic amount of TBTA (tris[(1-benzyl-1H-1,2,3-triazol-4-yl)methyl

An eco-compatible strategy for the diversity-oriented synthesis of macrocycles exploiting carbohydrate-derived building blocks

• Sushil K. Maurya and
• Rohit Rana

Beilstein J. Org. Chem. 2017, 13, 1106–1118, doi:10.3762/bjoc.13.110

• the iterative use of readily available sugar-derived alkyne/azide–alkene building blocks coupled through copper catalyzed azide–alkyne cycloaddition (CuAAC) reaction followed by pairing of the linear cyclo-adduct using greener reaction conditions. The eco-compatibility, mild reaction conditions

• the synthesis. The cyclization of the linear precursor is usually achieved by utilizing various ring-closing reactions such as Diels–Alder reactions, [15] aldol reactions, [16] copper-catalyzed azide–alkyne cycloaddition, [17][18] macrolactonization, macrolactamizations, Staudinger ligation or

• ] glycosides and macrocyclic glycolipids [11]. Similarly, the copper-catalyzed azide–alkyne cycloaddition (CuAAC) reaction has found wide application in medicinal chemistry [33], biology [34][35], polymer chemistry [36], carbohydrates [37][38][39][40], peptides [41][42][43][44] and in materials science [45][46

Nucleophilic and electrophilic cyclization of N-alkyne-substituted pyrrole derivatives: Synthesis of pyrrolopyrazinone, pyrrolotriazinone, and pyrrolooxazinone moieties

• Işıl Yenice,
• Sinan Basceken and
• Metin Balci

Beilstein J. Org. Chem. 2017, 13, 825–834, doi:10.3762/bjoc.13.83

• by a copper-catalyzed cross-coupling reaction. Nucleophilic cyclization of N-alkyne-substituted methyl 1H-pyrrole-2-carboxylates with hydrazine afforded the 6-exo-dig/6-endo-dig cyclization products depending on the electronic nature of the substituents attached to the alkyne. On the other hand

Transition-metal-catalyzed synthesis of phenols and aryl thiols

• Yajun Liu,
• Shasha Liu and
• Yan Xiao

Beilstein J. Org. Chem. 2017, 13, 589–611, doi:10.3762/bjoc.13.58

• phenols in water at room temperature. This catalyst can be reused many times without loss of the catalytic activity. Moreover, this catalyst could also be applied in the synthesis of anilines. 1.1.2 Copper-catalyzed hydroxylation of aryl halides: Copper catalysts are considered as economical and stable

• catalysts. However, copper catalysts often have a low catalytic activity to activate the C–Hal bond. Fortunately, along with the development of various bidentate ligands, the copper-catalyzed C–O coupling reaction has been extensively applied in the synthesis of phenols from aryl halides. However, the

• poorer efficiency of copper catalysts than that of palladium catalysts often limits the substrate scope to aryl iodides and aryl bromides. In 2009, two independent works by Taillerfer and You opened the prelude to the copper-catalyzed hydroxylation of aryl halides. The Taillefer group found that a

Pd- and Cu-catalyzed approaches in the syntheses of new cholane aminoanthraquinone pincer-like ligands

• Nikolay V. Lukashev,
• Gennadii A. Grabovyi,
• Dmitry A. Erzunov,
• Alexey V. Kazantsev,
• Gennadij V. Latyshev,
• Alexei D. Averin and
• Irina P. Beletskaya.

Beilstein J. Org. Chem. 2017, 13, 564–570, doi:10.3762/bjoc.13.55

• bile acids. High yields of arylaminocholanes were achieved in copper-catalyzed reactions of aryl iodides with 24-aminocholanes, while only a classical Pd-catalyzed protocol was suitable for the cross-coupling of aminocholanes and dichloroanthraquinones. The presence of hydroxy groups in the substrates

Fast and efficient synthesis of microporous polymer nanomembranes via light-induced click reaction

• Qi An,
• Youssef Hassan,
• Xiaotong Yan,
• Peter Krolla-Sidenstein,
• Tawheed Mohammed,
• Mathias Lang,
• Stefan Bräse and
• Manuel Tsotsalas

Beilstein J. Org. Chem. 2017, 13, 558–563, doi:10.3762/bjoc.13.54

• ]. Only few examples of soluble and therefore processable CMP materials are known, all limited to linear CMPs [13][14]. To overcome the issue of low processability, recently the group of Jiang and our group introduced the interfacial synthesis using an electro-activated approach [15] and a copper

• catalyzed azide–alkyne cycloaddition (CuAAC) approach, respectively [16]. These procedures are still limited to conductive substrates or associated with long reaction times. In this work, we present a novel strategy for the LbL synthesis of CMP thin films and nanomembranes, using the light-induced and