Solvent-free and room temperature synthesis of 3-arylquinolines from different anilines and styrene oxide in the presence of Al₂O₃/MeSO₃H

• Hashem Sharghi,
• Mahdi Aberi,
• Mohsen Khataminejad and
• Pezhman Shiri

Beilstein J. Org. Chem. 2017, 13, 1977–1981, doi:10.3762/bjoc.13.193

• been developed in the presence of Al2O3/MeSO3H via one-pot reaction of anilines and styrene oxide. This methodology provides very rapid access to 3-arylquinolines in good to excellent yields under solvent-free conditions at room temperature in air. Keywords: 3-arylquinolines; Al2O3; MeSO3H; one-pot

• anilines with styrene oxide via C–C cleavage is the efficient synthetic route to quinolones [1]. The reaction was performed using FeCl3 as catalyst in 1,4-dioxane as solvent at 110 °C for 12 h. According to the significance of this progress, we have decided to re-optimize it. The mixture of Al2O3 and

• styrene oxide at room temperature under solvent-free conditions (Scheme 1). Scheme 1 briefly compares the procedure reported by Wang and co-workers and our method. As it can be seen, the reaction can be performed under very short reaction time and low temperature. Results and Discussion To exploit

An efficient Pd–NHC catalyst system in situ generated from Na₂PdCl₄ and PEG-functionalized imidazolium salts for Mizoroki–Heck reactions in water

• Nan Sun,
• Meng Chen,
• Liqun Jin,
• Wei Zhao,
• Baoxiang Hu,
• Zhenlu Shen and
• Xinquan Hu

Beilstein J. Org. Chem. 2017, 13, 1735–1744, doi:10.3762/bjoc.13.168

• ) and styrene (2a) as the substrates, water as solvent and Na2PdCl4/L1 as the catalyst. The mixture of Na2PdCl4, L1 and base in water were preheated at 60 °C for 30 min before the addition of substrates [41]. The effect of base was first explored. As the selected experimental results illustrated in

• conditions in hand, we then further compared the catalytic performance of those Pd-complexes derived from phenyl and naphthyl analogues L2 and L3 with that of pyridine functionalized NHC precursor L1. A kinetic study of the coupling between 4-bromoacetophenone (1a) and styrene (2a) was performed in the

• the palladium complex in Mizoroki–Heck reactions. Furthermore, the TON of the coupling of 4-bromoacetophenone (1a) and styrene (2a) with Na2PdCl4/L1 as the catalyst was calculated to be 10,000, which is much higher than for previously reported catalytic systems under aqueous conditions. After

An effective Pd nanocatalyst in aqueous media: stilbene synthesis by Mizoroki–Heck coupling reaction under microwave irradiation

• Carolina S. García,
• Paula M. Uberman and
• Sandra E. Martín

Beilstein J. Org. Chem. 2017, 13, 1717–1727, doi:10.3762/bjoc.13.166

• - or 4-bromoacetophenone and styrene [47]. The best result with 4-bromoacetophenone was accomplished when the reaction was performed under MW irradiation for 10 minutes using 0.2 mol % of Pd, affording the (E)-stilbene product in 98% yield. In order to further explore the scope of the PVP-Pd NPs

• reaction of 4-bromoacetophenone (1a) and styrene (2a) as coupling reagents was initially selected to screening the reaction conditions (Table 1). In this case, the reactions were performed with 0.1 mol % of Pd, in a mixture of H2O/alcohol (3:1) as solvent under MW irradiation, employing a dynamic heating

• nanocatalyst. Thus, a variety of aryl halides 1a–h and olefins 2a–c were screened, employing the best reaction conditions above obtained (0.5 mmol of K2CO3, H2O/EtOH, at 130 ºC, Table 2). In all cases, clean and high selective reactions to obtain the trans-products were achieved. By using styrene (2a) and aryl

Encaging palladium(0) in layered double hydroxide: A sustainable catalyst for solvent-free and ligand-free Heck reaction in a ball mill

• Wei Shi,
• Jingbo Yu,
• Zhijiang Jiang,
• Qiaoling Shao and
• Weike Su

Beilstein J. Org. Chem. 2017, 13, 1661–1668, doi:10.3762/bjoc.13.160

• Information File 1). The Heck coupling reaction under HSBM conditions m-Bromoacetophenone (1a) and styrene (2a) were chosen as the model reactants (Scheme 2), catalyzed by Pd/MgAl-LDHs under ball-milling conditions with silica gel (5 g) and stainless-steel balls (ΦMB = 0.2, dMB = 14 mm) at 800 rpm. Based on

• and promote the reaction efficiently. Furthermore, the couplings of heteroaryl bromides (1m–o) and styrene (2a) as well as substituted bromobenzene (1i) and butyl acrylate (2f, 2g) were investigated to extend the scope and generality of the reaction. The results clearly demonstrate that all the

• substrates are well tolerated to give the corresponding coupling products smoothly with yields of 60–80%. Finally, the coupling reactions of aryl bromide 1i and styrene (2a) as well as heterocyclic bromide 1m and styrene (2a) were chosen as the model reactions under the optimized conditions to investigate

2-Methyl-2,4-pentanediol (MPD) boosts as detergent-substitute the performance of ß-barrel hybrid catalyst for phenylacetylene polymerization

• Julia Kinzel,
• Daniel F. Sauer,
• Marco Bocola,
• Marcus Arlt,
• Tayebeh Mirzaei Garakani,
• Andreas Thiel,
• Klaus Beckerle,
• Tino Polen,
• Jun Okuda and
• Ulrich Schwaneberg

Beilstein J. Org. Chem. 2017, 13, 1498–1506, doi:10.3762/bjoc.13.148

• III TOF/TOF mass spectrometer (Bruker Daltonics, Billerica, MA, US). GPC was measured on an Agilent Series 1100 (Midland, ON, Canada), equipped with two SDV linear N columns of 8 × 300 mm and 8 × 600 mm measures and 5 µm pore size, in THF at 30 °C against a poly(styrene) standard. Dynamic light

Photocatalyzed synthesis of isochromanones and isobenzofuranones under batch and flow conditions

• Manuel Anselmo,
• Lisa Moni,
• Hossny Ismail,
• Davide Comoretto,
• Renata Riva and
• Andrea Basso

Beilstein J. Org. Chem. 2017, 13, 1456–1462, doi:10.3762/bjoc.13.143

• carbocationic species. In addition, when diazonium salt 2i was reacted with styrene (3b), the formation of dihydroisoquinolinone 10 was not observed, while relatively unstable imidate 9 was detected. This observation supports our hypothesis that the nucleophilic attack to the intermediate A is taken by the

• amides. Reaction of o-alkoxycarbonyldiazonium salts with alkenes under Ru-photocatalyzed conditions. Proposed mechanism for the reaction of diazonium salt 2h with methyl methacrylate (3a). Reaction of 2-aminocarbonyldiazonium salt 2i with styrene (3b). Reaction of diazonium salts 11 with styrenes 12. The

Kinetic analysis of mechanoradical formation during the mechanolysis of dextran and glycogen

• Naoki Doi,
• Yasushi Sasai,
• Yukinori Yamauchi,
• Tetsuo Adachi,
• Masayuki Kuzuya and
• Shin-ichi Kondo

Beilstein J. Org. Chem. 2017, 13, 1174–1183, doi:10.3762/bjoc.13.116

• copolymers possessing synthetic polymers as branches. Sakaguchi et al. reported a diblock copolymer formation through the mechanochemical reaction of bacterial cellulose and methyl methacrylate in vacuum at 77 K [17]. Solala et al. studied the mechanochemical reaction of cotton in the presence of styrene and

NMR reaction monitoring in flow synthesis

• M. Victoria Gomez and
• Antonio de la Hoz

Beilstein J. Org. Chem. 2017, 13, 285–300, doi:10.3762/bjoc.13.31

• has been reported by Saggiomo and Velders [19] using 3D-printing technology. The authors described an easy two-step ABS (acrylonitrile butadiene styrene) scaffold removal method to obtain a 3D printed device inserted in a block of PDMS (polydimethylsiloxane). The authors tested this methodology for

Extrusion – back to the future: Using an established technique to reform automated chemical synthesis

• Deborah E. Crawford

Beilstein J. Org. Chem. 2017, 13, 65–75, doi:10.3762/bjoc.13.9

• sequential postsynthetic modification of polystyrene by isoprene [16]. The authors focus mainly on the engineering aspects of the project rather than the chemical reaction itself. The first part of the process involves the chemical reaction between styrene and s-BuLi, which is employed as an initiator

• (Scheme 1). The s-BuLi reacts with the double bond of styrene, initiating a homopolymerisation process. Once all the monomer is consumed, the polymer has a stable anionic polymer chain, which allows for further functionalisation by reaction with electrophilic functional groups. The solution-based living

• large scale. Furthermore, Höcker et al. report the post polymerisation of polystyrene with isoprene, which is actually carried out in the same processing line as the polymerisation of styrene, i.e., styrene is polymerised initially in the extruder barrel and isoprene is fed into the barrel at a later

Methylenelactide: vinyl polymerization and spatial reactivity effects

• Judita Britner and
• Helmut Ritter

Beilstein J. Org. Chem. 2016, 12, 2378–2389, doi:10.3762/bjoc.12.232

• polymerization of the cyclic push–pull-type monomer methylenelactide in comparison to the non-cyclic monomer α-acetoxyacrylate is described. The experimental results revealed that methylenelactide undergoes a self-initiated polymerization. The copolymerization parameters of methylenelactide and styrene as well

• copolymerization of MLA with styrene and methyl methacrylate, respectively. The results were compared to the well-known push–pull type monomer α-acetoxyacrylate. Results and Discussion Free-radical polymerization of methylenelactide MLA The push–pull type monomer MLA contains an electron-deficient vinyl group

• copolymerization parameters of MLA with styrene and MMA, respectively were evaluated through the method of Kelen and Tüdös [18]. For this, the residual monomer ratio was determined by high performance liquid chromatography (see execution, characterization methods and Figures S14 and S15 in Supporting Information

Enantioconvergent catalysis

• Justin T. Mohr,
• Jared T. Moore and
• Brian M. Stoltz

Beilstein J. Org. Chem. 2016, 12, 2038–2045, doi:10.3762/bjoc.12.192

• (Aspergillus niger and Beauveria sulfurescens) were capable of resolving racemic styrene oxide (31, Scheme 7) by hydrolytic kinetic resolution [35]. It was recognized that these two biocatalysts exhibited opposite enantiomer preference in the kinetic resolution event. Moreover, the major hydrolysis byproduct

Ionic liquids as transesterification catalysts: applications for the synthesis of linear and cyclic organic carbonates

• Maurizio Selva,
• Alvise Perosa,
• Sandro Guidi and
• Lisa Cattelan

Beilstein J. Org. Chem. 2016, 12, 1911–1924, doi:10.3762/bjoc.12.181

• acidic polyionic liquid by the copolymerization of a zwitterionic liquid based on vinylpyridinium, styrene and ethyleneglycol dimethacrylate (Scheme 4) [44]. The resulting PIL with particle sizes of about 0.5–3 mm, was an efficient catalyst for a series of esterification reactions of different acids

On the cause of low thermal stability of ethyl halodiazoacetates

• Magnus Mortén,
• Martin Hennum and
• Tore Bonge-Hansen

Beilstein J. Org. Chem. 2016, 12, 1590–1597, doi:10.3762/bjoc.12.155

• investigated the reactivity of the carbenes generated thermally at ambient temperature in a non-catalytic fashion. As a probe, we elected the standard cyclopropanation reaction of styrenes. We found that the presence of styrene and/or methyl 4-nitrobenzoate (internal standard) did not change the rate of the

• a screw cap was added dry CH2Cl2 (1 mL), styrene (146 mg, 1.40 mmol, 2.1 equiv), Rh2(esp)2 (8.5 mg, 0.011 mmol, 0.02 equiv) and a magnetic stirring bar. To the stirred mixture was added a solution of 2b in CH2Cl2 (7.00 mL, 0.68 mmol, 1.0 equiv). The vial was capped and left stirring at room

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

• –R2 = (CH2)4] typical Heck reaction conditions employing styrene as olefin component not only led to the desired styrene derivative B but mainly to the cyclized product C. If the reaction was performed without the olefin it provided only the tertiary alcohol C in reasonable yield [5]. Similar C–C bond

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

• ] and PCy3 formed the ruthenium(0) complex, which then mediated the oxidative coupling of N-benzyl-protected isatin and styrene to form oxametallacycle I. The ruthenium alkoxide III was formed through two possible pathways: (a) the direct transfer hydrogenolytic cleavage of I (slow); (b) the

Superstructures with cyclodextrins: chemistry and applications III

• Gerhard Wenz and
• Eric Monflier

Beilstein J. Org. Chem. 2016, 12, 937–938, doi:10.3762/bjoc.12.91

• styrene from ethylbenzene [3][4]. Highly porous networks were synthesized by crosslinking β-CD with tetrafluoroterephthalonitrile. These networks were able to almost completely remove pollutants (e.g., bisphenol A) within a short time from wastewater [5]. Stimuli-responsive nanoparticles were assembled by

Aluminacyclopentanes in the synthesis of 3-substituted phospholanes and α,ω-bisphospholanes

• Vladimir A. D’yakonov,
• Alevtina L. Makhamatkhanova,
• Rina A. Agliullina,
• Leisan K. Dilmukhametova,
• Tat’yana V. Tyumkina and
• Usein M. Dzhemilev

Beilstein J. Org. Chem. 2016, 12, 406–412, doi:10.3762/bjoc.12.43

• (31P13C5) observed in the 13С NMR spectra increase to ca. 53–66 Hz. When styrene or 2-vinylnaphthalene reacts with AlEt3 in the presence of Cp2ZrCl2, apart from 3-phenyl(naphthyl)-1-ethylaluminacyclopentanes 5a–f, the reaction mixture contains 2-phenyl(naphthyl)-1-ethylaluminacyclopentane 6a–f [21]. Both

Amino-functionalized (meth)acryl polymers by use of a solvent-polarity sensitive protecting group (Br-t-BOC)

• Helmut Ritter,
• Monir Tabatabai and
• Markus Herrmann

Beilstein J. Org. Chem. 2016, 12, 245–252, doi:10.3762/bjoc.12.26

• Scharmbeck SFD (Model S5200) sampler. A Waters 486 Turnable Absorbance Detector and a Scharmbeck SFD RI 2000 detector were used for detection. A set of columns packed with porous styrene–divinylbenzene-copolymer beads was used for separation of the analytes (MZ Analysentechnik GmbH, 1 × guard column 100 Å, 3

Hydroquinone–pyrrole dyads with varied linkers

• Hao Huang,
• Christoffer Karlsson,
• Maria Strømme,
• Martin Sjödin and
• Adolf Gogoll

Beilstein J. Org. Chem. 2016, 12, 89–96, doi:10.3762/bjoc.12.10

• in their study, ten equivalents of styrene were used to obtain 28% yield, indicating that the reaction conditions were not optimal, and therefore cannot be applied to other vinyl substrates such as dimethoxystyrene directly. A synthetic route via hydrogenation of the ethynyl linker compound 4d was

Copper-catalyzed intermolecular oxyamination of olefins using carboxylic acids and O-benzoylhydroxylamines

• Brett N. Hemric and
• Qiu Wang

Beilstein J. Org. Chem. 2016, 12, 22–28, doi:10.3762/bjoc.12.4

• use of pentafluorobenzoic acid (1a) as the oxygen source and 4-benzoyloxymorpholine (3a) as the nitrogen source in the proposed intermolecular oxyamination of styrene (2a, Table 1). Copper was found to be effective and critical to promote the formation of oxyamination product 4a with excellent

• the amine 5e can be readily cleaved for the construction of a secondary amine. Finally, the scope of olefins for the transformation was examined including both aryl and alkyl olefins (Table 2). First, styrene derivatives bearing a variety of substitutions on the aryl ring, including both electron

• -donating and electron-withdrawing groups, were all effective in providing the 1,2-oxyaminated products with exclusive regioselectivity (Table 2, entries 1–6). Interestingly, the products derived from electron-rich styrene substrates (i.e., 6a, 6b, 6e) were formed in higher yields than those from electron

New metathesis catalyst bearing chromanyl moieties at the N-heterocyclic carbene ligand

• Agnieszka Hryniewicka,
• Szymon Suchodolski,
• Agnieszka Wojtkielewicz,
• Jacek W. Morzycki and
• Stanisław Witkowski

Beilstein J. Org. Chem. 2015, 11, 2795–2804, doi:10.3762/bjoc.11.300

• ) gave also SM products besides the desired CM products. Furthermore, more dimeric products gave allyloxybenzene than hex-5-enyl acetate. It is worth noting that the CM reaction between styrene and (Z)-but-2-ene-1,4-diol diacetate (entry 1, Table 2) was highly efficient (97% yield) using catalyst 9

Recent advances in metathesis-derived polymers containing transition metals in the side chain

• Ileana Dragutan,
• Valerian Dragutan,
• Bogdan C. Simionescu,
• Albert Demonceau and
• Helmut Fischer

Beilstein J. Org. Chem. 2015, 11, 2747–2762, doi:10.3762/bjoc.11.296

• the atom-transfer radical polymerization of methyl methacrylate or styrene to obtain poly(methyl methacrylate) and polystyrene devoid of colored traces of catalyst, a very important requirement for special applications, e.g., in dentistry, medical devices, housewares, and food packaging. In another

Copper-catalyzed aminooxygenation of styrenes with N-fluorobenzenesulfonimide and N-hydroxyphthalimide derivatives

• Yan Li,
• Xue Zhou,
• Guangfan Zheng and
• Qian Zhang

Beilstein J. Org. Chem. 2015, 11, 2721–2726, doi:10.3762/bjoc.11.293

•  1). Initially, we conducted the three-component amnooxygenation of styrene 1a with NFSI and NHPI (2a). After the reaction of 1a (0.3 mmol), NFSI (0.3 mmol, 1.0 equiv) and 2a (0.45 mmol, 1.5 equiv) was performed in the presence of Cu(OTf)2 (10 mol %) in dichloromethane (DCM, 2 mL) under nitrogen

• , the oxidation of Cu(I) with NFSI provided F–Cu(III)–N complex I, which could transform into a copper(II)-stabilized benzenesulfonimide radical II through a redox isomerization equilibrium. Next, the intermolecular radical addition of II to styrene 1g took place, producing benzylic radical III and Cu

Selectively fluorinated cyclohexane building blocks: Derivatives of carbonylated all-cis-3-phenyl-1,2,4,5-tetrafluorocyclohexane

• Mohammed Salah Ayoup,
• David B. Cordes,
• Alexandra M. Z. Slawin and
• David O'Hagan

Beilstein J. Org. Chem. 2015, 11, 2671–2676, doi:10.3762/bjoc.11.287

• a mixture of stilbene isomers 16. Direct hydrogenation of the mixture afford dihydrostilbene 17 as a crystalline solid, a structure which was confirmed by X-ray crystallography and is shown in the inset in Scheme 3. Aldehyde 15 could also be converted to styrene 18 in good yield using the Simmons

Copper-catalyzed stereoselective conjugate addition of alkylboranes to alkynoates

• Takamichi Wakamatsu,
• Kazunori Nagao,
• Hirohisa Ohmiya and
• Masaya Sawamura

Beilstein J. Org. Chem. 2015, 11, 2444–2450, doi:10.3762/bjoc.11.265

• mode. The syn stereoselectivity was excellent regardless of the substrate structure, and a variety of functional groups were tolerated in both the alkylborane and the alkynoate. Results and Discussion Alkylborane 2a (0.275 mmol), which was obtained via hydroboration of styrene (1a) with the 9

• alkylboranes through in situ alkene hydroboration is an attractive feature of this protocol and various functional groups are tolerated in both the alkylborane and alkynoate substrates. Experimental The reaction shown in Scheme 1 was conducted in a similar manner as described before [15]. Styrene (1a, 33 μL