A novel and robust heterogeneous Cu catalyst using modified lignosulfonate as support for the synthesis of nitrogen-containing heterocycles

• Bingbing Lai,
• Meng Ye,
• Ping Liu,
• Minghao Li,
• Rongxian Bai and
• Yanlong Gu

Beilstein J. Org. Chem. 2020, 16, 2888–2902, doi:10.3762/bjoc.16.238

• , ring-closing, metathesis, cycloadditions, radical reactions and microwave-assisted reactions [38][39][40]. In this work, we attempt to develop a greener, simpler, more efficient and recyclable system to synthesize arylpyridine derivatives. Initially, the reaction of acetophenone (5a) and 1,3

Fluorine effect in nucleophilic fluorination at C4 of 1,6-anhydro-2,3-dideoxy-2,3-difluoro-β-D-hexopyranose

• Danny Lainé,
• Vincent Denavit,
• Olivier Lessard,
• Laurie Carrier,
• Charles-Émile Fecteau,
• Paul A. Johnson and
• Denis Giguère

Beilstein J. Org. Chem. 2020, 16, 2880–2887, doi:10.3762/bjoc.16.237

• . Nevertheless, we investigated the preparation of 1,6-anhydro-2,3,4-trideoxy-2,3,4-trifluoro-β-ᴅ-hexopyranose analogues from previously described 1,6-anhydro-2,3-dideoxy-2,3-difluoro-β-ᴅ-hexopyranoses 2–5 using DAST (Table 1). We thus used 2 equivalents of DAST at 100 °C under microwave heating for 1 h and

Selective and reversible 1,3-dipolar cycloaddition of 6-aryl-1,5-diazabicyclo[3.1.0]hexanes with 1,3-diphenylprop-2-en-1-ones under microwave irradiation

• Alexander P. Molchanov,
• Mariia M. Efremova,
• Mariya A. Kryukova and
• Mikhail A. Kuznetsov

Beilstein J. Org. Chem. 2020, 16, 2679–2686, doi:10.3762/bjoc.16.218

• cycloaddition of in situ-generated azomethine imine under microwave conditions is described. The reaction of 6-aryl-1,5-diazabicyclo[3.1.0]hexanes with 1,3-diphenylprop-2-en-1-ones proceeds regio- and stereoselectively giving mostly good yields of the corresponding perhydropyrazolopyrazoles. The products of the

• that the Lewis acid-catalyzed reaction of diaziridines with donor–acceptor cyclopropanes and aziridines affords the perhydropyridazine or triazine derivatives, respectively, in good yields [31][32][33]. The use of microwave irradiation in organic synthesis complies with the principles of green

• chemistry and has attracted much interest. For 1,3-dipolar cycloaddition reactions microwave irradiation not only allows to reduce the reaction time and to increase yields, but in some cases also can affect the selectivity of the reaction [34][35][36]. The efficiency of microwave irradiation has been shown

Synthesis and characterization of S,N-heterotetracenes

• Astrid Vogt,
• Florian Henne,
• Christoph Wetzel,
• Elena Mena-Osteritz and
• Peter Bäuerle

Beilstein J. Org. Chem. 2020, 16, 2636–2644, doi:10.3762/bjoc.16.214

• 3-nitro-2,2’-bithiophene with triethyl phosphite under microwave irradiation and surprisingly obtained targeted heterotriacene H-DTP (vide supra) with only 11% yield [45]. This result prompted us to have a closer look on the applicability of the Cadogan reaction/cyclization in order to provide S,N

Styryl-based new organic chromophores bearing free amino and azomethine groups: synthesis, photophysical, NLO, and thermal properties

• Anka Utama Putra,
• Deniz Çakmaz,
• Nurgül Seferoğlu,
• Alberto Barsella and
• Zeynel Seferoğlu

Beilstein J. Org. Chem. 2020, 16, 2282–2296, doi:10.3762/bjoc.16.189

• was performed using a Thermo Scientific Flash 2000 analyzer at the Gazi University Department of Chemistry. The microwave syntheses were carried out in a Milestone Start microwave reaction system. The melting points were measured using an Electrothermal IA9200 apparatus. Absorption spectra were

The B & B approach: Ball-milling conjugation of dextran with phenylboronic acid (PBA)-functionalized BODIPY

• Patrizia Andreozzi,
• Lorenza Tamberi,
• Elisamaria Tasca,
• Gina Elena Giacomazzo,
• Marta Martinez,
• Mirko Severi,
• Marco Marradi,
• Stefano Cicchi,
• Sergio Moya,
• Giacomo Biagiotti and
• Barbara Richichi

Beilstein J. Org. Chem. 2020, 16, 2272–2281, doi:10.3762/bjoc.16.188

• accurately weighted amount of each sample was treated with a microwave-assisted digestion (CEM MARS Xpress) using 1 mL of suprapure HNO3 obtained by sub-boiling distillation and 1 mL of suprapure H2O2. Each sample was thus diluted to 10 mL with Ultrapure water (UHQ), spiked with 0.5 ppm of Ge used as an

Synthetic approaches to bowl-shaped π-conjugated sumanene and its congeners

• Shakeel Alvi and
• Rashid Ali

Beilstein J. Org. Chem. 2020, 16, 2212–2259, doi:10.3762/bjoc.16.186

• crystal of sumanene derivative 82 by means of time-resolved microwave conductivity technique. On the other hand, four years later, Sakurai and his teammates have reported the selective synthesis of diverse monosubstituted sumanene derivatives by employing electrophilic aromatic substitution reactions as

• using trifluoroacetyl nitrate which was in situ generated from conc. HNO3 and trifluoroacetic anhydride. On the other hand, formylation and acetylation were performed under microwave conditions at 130 °C using triflic anhydride and DMF or dimethylacetamide (DMA) to deliver the corresponding

• Suzuki–Miyaura cross-coupling reaction of bromosumanene 82 under microwave reaction conditions. Whereas another route involves the Ni-catalyzed aryl–aryl homo-coupling between the two molecules of iodosumanene 79 [51][52]. Moreover, the bissumanenyl 92, which is thought to be chiral because of the two

Naphthalene diimide bis-guanidinio-carbonyl-pyrrole as a pH-switchable threading DNA intercalator

• Poulami Jana,
• Filip Šupljika,
• Carsten Schmuck and
• Ivo Piantanida

Beilstein J. Org. Chem. 2020, 16, 2201–2211, doi:10.3762/bjoc.16.185

• . Microwave-assisted SPPS was carried out using a CEM Discover system. 1H and 13C NMR spectra were recorded on a DRX 500 MHz Bruker spectrometer at ambient temperature. Chemical shifts (δ) are expressed in parts per million and J values in hertz. The following abbreviations were used for peak multiplicities

Synergy between supported ionic liquid-like phases and immobilized palladium N-heterocyclic carbene–phosphine complexes for the Negishi reaction under flow conditions

• Edgar Peris,
• Raúl Porcar,
• María Macia,
• Jesús Alcázar,
• Eduardo García-Verdugo and
• Santiago V. Luis

Beilstein J. Org. Chem. 2020, 16, 1924–1935, doi:10.3762/bjoc.16.159

• of methylimidazolium units leading to a Pd(II)-SILLP system 11 with 0.56 mequiv of Pd/g of SILLP and 3.79 mequiv of IL-like units/g of SILLP (Scheme 4). This system was treated with either NaBH4 or EtOH under microwave irradiation to produce the corresponding PdNPs immobilized onto SILLPs (12a,b

Tuneable access to indole, indolone, and cinnoline derivatives from a common 1,4-diketone Michael acceptor

• Dalel El-Marrouki,
• Sabrina Touchet,
• Abderrahmen Abdelli,
• Hédi M’Rabet,
• Mohamed Lotfi Efrit and
• Philippe C. Gros

Beilstein J. Org. Chem. 2020, 16, 1722–1731, doi:10.3762/bjoc.16.144

• as the main product, with the best yield being obtained in butanol (43%, Table 1, entry 11), however, with the formation of 6b occurring only in 10% yield. Switching to microwave irradiation formed exclusively 7b in 60% yield after 3 h (Table 1, entry 13). Note, that to check the effect of a shorter

• achieve the conformation of the proposed intermediate. We next examined the preparation of a set of indolones under the microwave conditions determined in Table 1, entry 13. These conditions were applied to several amines, producing exclusively the corresponding substituted indolones 7d and 7g–k in 48–56

Microwave-assisted efficient one-pot synthesis of N²-(tetrazol-5-yl)-6-aryl/heteroaryl-5,6-dihydro-1,3,5-triazine-2,4-diamines

• Moustafa Sherief Moustafa,
• Ramadan Ahmed Mekheimer,
• Saleh Mohammed Al-Mousawi,
• Mohamed Abd-Elmonem,
• Hesham El-Zorba,
• Afaf Mohamed Abdel Hameed,
• Tahany Mahmoud Mohamed and
• Kamal Usef Sadek

Beilstein J. Org. Chem. 2020, 16, 1706–1712, doi:10.3762/bjoc.16.142

• developed by reacting 5-amino-1,2,3,4-tetrazole with aromatic aldehydes and cyanamide in pyridine under controlled microwave heating with high yields. X-ray crystallography confirmed the structure of the obtained products. Keywords: microwave irradiation; N2-(tetrazol-5-yl)-6-aryl/heteroaryl-1,3,5-triazine

• green methodologies in synthetic heterocyclic chemistry. The utilization of microwave heating as an energy source has several advantages including operational simplicity, high reaction yields, enhanced rates, and increased energy efficiency [34][35][36][37][38][39][40]. In continuation of our efforts in

• 5-aminotetrazole (3) in pyridine under controlled microwave heating (Scheme 2). Results and Discussion With the initial aim of optimizing the reaction conditions, we began our study by reacting equimolar amounts of cyanamide 1, aromatic aldehydes 2, and 5-aminotetrazole (3) in pyridine and the

Pauson–Khand reaction of fluorinated compounds

• Jorge Escorihuela,
• Daniel M. Sedgwick,
• Alberto Llobat,
• Mercedes Medio-Simón,
• Pablo Barrio and
• Santos Fustero

Beilstein J. Org. Chem. 2020, 16, 1662–1682, doi:10.3762/bjoc.16.138

• endotermic process is the rate-limiting step and long reaction times are generally associated to this. However, the reaction can be accelerated in conditions that facilitate the dissociation of CO ligands such as heating, microwave irradiation [37][38], visible light, or ultrasonication [39]. Alternatively

• cyclohexene, maleic anhydride, ethylene carbonate, and 1-octene, the desired products were not formed under the reaction conditions. In the same year, Helaja and co-workers examined the electronic effects of the alkyne substituent on the regioselectivity of the microwave-assisted PKR with norbornene [80]. The

The McKenna reaction – avoiding side reactions in phosphonate deprotection

• Katarzyna Justyna,
• Joanna Małolepsza,
• Damian Kusy,
• Waldemar Maniukiewicz and
• Katarzyna M. Błażewska

Beilstein J. Org. Chem. 2020, 16, 1436–1446, doi:10.3762/bjoc.16.119

• be performed either at room temperature, in refluxing CH2Cl2 [19][28][29], at higher temperatures [1][30][31], and also under microwave conditions [32][33][34]. At lower temperatures or shorter reaction times an incomplete transesterification was reported [35]. The use of the low-boiling CH2Cl2 at

Recent synthesis of thietanes

• Jiaxi Xu

Beilstein J. Org. Chem. 2020, 16, 1357–1410, doi:10.3762/bjoc.16.116

Oxime radicals: generation, properties and application in organic synthesis

• Igor B. Krylov,
• Stanislav A. Paveliev,
• Alexander S. Budnikov and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2020, 16, 1234–1276, doi:10.3762/bjoc.16.107

Activated carbon as catalyst support: precursors, preparation, modification and characterization

• Melanie Iwanow,
• Tobias Gärtner,
• Volker Sieber and
• Burkhard König

Beilstein J. Org. Chem. 2020, 16, 1188–1202, doi:10.3762/bjoc.16.104

• be produced by salt templating or ultrasonic spray pyrolysis as well as by microwave irradiation. The resulting activated carbon materials are characterized by a variety of techniques such as SEM, FTIR, nitrogen adsorption, Boehm titrations, adsorption of phenol, methylene blue and iodine, TPD, CHNS

• ]. Comparison of conventional and microwave heating Conventional heating for physical or chemical activation of the precursor materials has several drawbacks such as the non-uniform heating of the samples or a high energy demand due to long carbonization and activation times at high temperatures [103][104

• ]. Microwave irradiation is a promising alternative with some advantages. In contrast to conventional heating, which is based on the convection mechanism involving conduction and radiation, the sample can be heated uniformly and contactless by the heat generated from electromagnetic energy, resulting in

Fluorinated phenylalanines: synthesis and pharmaceutical applications

• Laila F. Awad and
• Mohammed Salah Ayoup

Beilstein J. Org. Chem. 2020, 16, 1022–1050, doi:10.3762/bjoc.16.91

• product 2-[18F]FPhe 46 in 43% yield, whereas under microwave irradiation a 34% yield was obtained. Under the optimized conditions, the enantiomeric purity was reported to be ≥94% ee [46] (Scheme 10). 1.3. Photooxidative cyanation of fluorinated benzylamine A convenient, protecting group-free, and

Diversity-oriented synthesis of 17-spirosteroids

• Benjamin Laroche,
• Thomas Bouvarel,
• Martin Louis-Sylvestre and
• Bastien Nay

Beilstein J. Org. Chem. 2020, 16, 880–887, doi:10.3762/bjoc.16.79

• microwave irradiations. Taking advantage of the propargyl alcohol moiety present on commercially available steroids, this classical strategy was applied to mestranol and lynestrenol, giving a collection of new complex 17-spirosteroids. Keywords: diversity-oriented strategy; 17-ethynyl-17-hydroxysteroids

• Stewart–Grubbs catalyst combined with microwave heating at 120 °C (allyl ethers) or 170 °C (4-pentenyl ethers), demonstrating improved yields [77]. These temperatures were needed for the reaction to quickly go to completion. With 17-O-allylmestranol (5a), a rapid screening of the Stewart–Grubbs (SG

• study (Scheme 2). Thus, in the presence of G-II in toluene and under microwave heating, the reaction provided 17-spirosteroid dienes 8–10 in good yields (67–82%). Spirocyclic vinylcyclopentene substrates 8a,b and 9a,b were engaged in Diels–Alder reactions with a variety of dienophiles (11–15). The

Efficient synthesis of piperazinyl amides of 18β-glycyrrhetinic acid

• Dong Cai,
• ZhiHua Zhang,
• Yufan Meng,
• KaiLi Zhu,
• LiYi Chen,
• ChangXiang Yu,
• ChangWei Yu,
• ZiYi Fu,
• DianShen Yang and
• YiXia Gong

Beilstein J. Org. Chem. 2020, 16, 798–808, doi:10.3762/bjoc.16.73

• using conventional or microwave methods had no effect on the conversion of intermediate 6 to compound 8. To explain the stable structure of the intermediate 6 (Figure 2a), energy minimization by MM2 was performed using the ChemBio3D Ultra 14.0 (CambridgeSoft Corporation, 2014) software force field [22

• yields (<19%) of the desired compound 8 were obtained after a longer reaction time (Table 2, entries 1–4). A further investigation of the reaction using microwave irradiation to heat at reflux temperature also failed to produce the target product (Table 2, entry 2). The intermediate 6 exhibited very low

One-pot synthesis of dicyclopenta-fused peropyrene via a fourfold alkyne annulation

• Ji Ma,
• Yubin Fu,
• Junzhi Liu and
• Xinliang Feng

Beilstein J. Org. Chem. 2020, 16, 791–797, doi:10.3762/bjoc.16.72

• solvents, such as dichloromethane, chloroform, tetrahydrofuran and toluene, allowing a full characterization by NMR analyses. Finally, the palladium-catalyzed cyclopentannulation of compound 5 with 1,2-diphenylethyne under microwave conditions using the catalyst system of [Pd2(dba)3] and P(o-tol)3 afforded

• -diphenylethyne, Pd2(dba)3, P(o-tol)3, KOAc, LiCl, DMF, 130 °C, microwave, 6 h, 5%. Supporting Information Supporting Information File 276: Experimental details, synthetic procedures, single crystal X-ray data for 1, detailed theoretical calculations, and analytical data for the compounds. Acknowledgements We

Synthesis of C₇₀-fragment buckybowls bearing alkoxy substituents

• Yumi Yakiyama,
• Shota Hishikawa and
• Hidehiro Sakurai

Beilstein J. Org. Chem. 2020, 16, 681–690, doi:10.3762/bjoc.16.66

• using 20 mol % of Pd(PPh3)2Cl2 and 150 mol % DBU in DMF at 150 °C under microwave irradiation conditions to afford the desired dimethoxy derivative 5a in 75% yield. In contrast, when the reaction of 4b was performed, not only the desired product 5b but also the unexpected regioisomer 5c was obtained

• . The temperature dependency of the product ratio between 5b and 5c was investigated and the results are shown in Table 1. The cyclization did not proceed under 140 °C, and at 140 °C the total yield is low (41% after 40 min microwave irradiation) but the ratio of 5b was the highest (5b/5c = 10:1). The

• microwave experiment was carried out with a Biotage Initiator Eight EXP. UV–vis absorption spectra were recorded on a JASCO V-670 spectrometer and a SHIMADZU UV-1800 spectrometer. Fluorescence spectra were recorded on a JASCO FP-6500 spectrometer. Melting points were determined on a Stanford Research

Microwave-assisted efficient and facile synthesis of tetramic acid derivatives via a one-pot post-Ugi cascade reaction

• Yong Li,
• Zheng Huang,
• Jia Xu,
• Yong Ding,
• Dian-Yong Tang,
• Jie Lei,
• Hong-yu Li,
• Zhong-Zhu Chen and
• Zhi-Gang Xu

Beilstein J. Org. Chem. 2020, 16, 663–669, doi:10.3762/bjoc.16.63

• University of Arts and Sciences, Chongqing 402160, China Department of Pharmaceutical Sciences, College of Pharmacy, University of Arkansas for Medical Sciences, Little Rock, AR 72205, USA 10.3762/bjoc.16.63 Abstract A facile microwave-assisted method for the synthesis of tetramic acid derivatives has been

• developed through an Ugi/Dieckmann cyclization strategy with DBU. This two-step one-pot procedure afforded the targeted tetramic acid analogues in good yields. With commercially available Ugi starting materials, microwave irradiation, a simple operation, excellent yields, and a broad scope, this reaction

• investigated the effect of different inorganic and organic bases (Table 1). It was interesting to note that all of the bases tested in the study afforded the desired enol tetramic acid derivative 7a after the reaction was heated under the microwave irradiation conditions. The ketone compound 6a could be the

A systematic review on silica-, carbon-, and magnetic materials-supported copper species as efficient heterogeneous nanocatalysts in “click” reactions

• Pezhman Shiri and
• Jasem Aboonajmi

Beilstein J. Org. Chem. 2020, 16, 551–586, doi:10.3762/bjoc.16.52

• condensation of phenylacetylene and 1‐azido‐4‐nitrobenzene on a 4 mmol scale in EtOH/H2O (1:1) using 5 mol % of 87 was performed. After completion of the reaction, the heterogeneous catalyst was centrifuged and washed with ethyl acetate/water. This nanocatalyst could be reused in up to ten cycles. A microwave

• , trimethylsilylacetylene (TMSA) was selected for coupling with aryl iodides in the presence of a catalytic amount of Pd–Cu/C and PPh3 using Et2NH as a base in methanol at 120 °C under microwave irradiation for 20 min. In the next step, the azide derivative was added to the reaction mixture. Finally, the reaction mixture

Aerobic synthesis of N-sulfonylamidines mediated by N-heterocyclic carbene copper(I) catalysts

• Faïma Lazreg,
• Marie Vasseur,
• Alexandra M. Z. Slawin and
• Catherine S. J. Cazin

Beilstein J. Org. Chem. 2020, 16, 482–491, doi:10.3762/bjoc.16.43

• , 58.39; H, 6.16; N, 6.08. 1-{2,6-(Diisopropyl)phenyl}-3-methyl-4-(4-tert-butylphenyl)-1,2,3-triazol-5-ylidene-(N,N’-bis{2,6-(diisopropyl)phenyl}imidazol-2-ylidene)copper(I) tetrafluoroborate, [Cu(IPr)(Triaz)]BF4 (5). In a glovebox, a microwave vial was charged with [Cu(Cl)(IPr)] (200.0 mg, 0.41 mmol

• ), NaOH (66.0 mg, 4 equiv, 1.64 mmol), Triaz.HBF4 (190.0 mg, 1 equiv, 0.41 mmol) and acetonitrile (2 mL). The reaction mixture was stirred during 2 h at 80 °C in a microwave. The solution was concentrated and diethyl ether (10 mL) was added. The precipitate was collected by filtration and washed with

• ). In a glovebox, a vial was charged with [Cu(Cl)(Triaz)] (150.0 mg, 0.32 mmol), NaOH (50 mg, 4 equiv, 1.28 mmol), Triaz.HBF4 (148 mg, 1 equiv, 0.32 mmol) and acetonitrile (2 mL). The reaction mixture was stirred during 2 h at 80 °C in a microwave. The solution was concentrated (0.5 mL) and diethyl

Architecture and synthesis of P,N-heterocyclic phosphine ligands

• Wisdom A. Munzeiwa,
• Bernard Omondi and
• Vincent O. Nyamori

Beilstein J. Org. Chem. 2020, 16, 362–383, doi:10.3762/bjoc.16.35

• bipyridyl- (6), quinolinyl- (7), phenanthrolinyl- (8) and terpyridinyl- (9) phosphine ligands (Figure 1) [60]. Trofimov et al. [61][62] reported on an alternative reaction pathway using microwave heating for the synthesis of tris(2-pyridyl)phosphine in which white and red phosphorus were used. On treating

• treated with triflic anhydride to afford the corresponding triflate 55. Microwave-assisted reduction of compound 55 with pyridinium chloride afforded the α-chloropyridine derivative 56, which was further catalytically dehalogenated with palladium on carbon and formic acid to generate the pyridine scaffold