Thermophilic phosphoribosyltransferases Thermus thermophilus HB27 in nucleotide synthesis

• Ilja V. Fateev,
• Ekaterina V. Sinitsina,
• Aiguzel U. Bikanasova,
• Maria A. Kostromina,
• Elena S. Tuzova,
• Larisa V. Esipova,
• Tatiana I. Muravyova,
• Alexei L. Kayushin,
• Irina D. Konstantinova and
• Roman S. Esipov

Beilstein J. Org. Chem. 2018, 14, 3098–3105, doi:10.3762/bjoc.14.289

• , acrylamide, N,N'-bisacrylamide, ATP, bromophenol blue, agarose, EDTA, IPTG, ampicillin, sodium dodecylsulfate, imidazole and DMF were purchased from Panreac (Spain, Barselona). Ethanol was purchased from MedChemProm. Coomassie Brilliant Blue R-250 was purchased from Bio-Rad (USA, CA). Bacto yeast extract

Olefin metathesis catalysts embedded in β-barrel proteins: creating artificial metalloproteins for olefin metathesis

• Daniel F. Sauer,
• Johannes Schiffels,
• Takashi Hayashi,
• Ulrich Schwaneberg and
• Jun Okuda

Beilstein J. Org. Chem. 2018, 14, 2861–2871, doi:10.3762/bjoc.14.265

• catalyst or redox catalyst. Various metalloenzymes have been applied in laboratory-scale reactions and a few metalloenzymes such as nitrile hydratase (cobalt(III) in the active site) for the production of acrylamide have found application in industry [25]. Notably, however, the reaction scope of natural

Cobalt- and rhodium-catalyzed carboxylation using carbon dioxide as the C1 source

• Tetsuaki Fujihara and
• Yasushi Tsuji

Beilstein J. Org. Chem. 2018, 14, 2435–2460, doi:10.3762/bjoc.14.221

• corresponding product 19f-Me in good yield. Methyl, ethyl, and tert-butyl acrylates 18b, 18c, and 18d, respectively, also afforded the corresponding products. The product of the reaction with acrylamide 18e was also obtained. Scheme 19 shows a plausible reaction mechanism for this four-component coupling

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

• based on poly(acrylamide-co-acryl acid) (poly(AAm-co-AAc)) [117]. These nanogels were transformed into their catalytic counterparts by growing silver nanoparticles (Ag NPs) inside the cross-linked polymeric network. These catalytic nanogels were also used to catalyse the reduction of 4-nitrophenol to 4

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

• bearing an acrylamide group at the ortho-position of the benzene ring. Synthesis of parent chiral benzamides 6–8 The use of a stereoselective chiral auxiliary which could be incorporated and removed easily without racemization was crucial for the success of our strategy. These requirements prompted us to

• bearing an array of acrylamide groups (Scheme 3). Substrate 6a bearing a (R)-α-methylbenzyl chiral auxiliary led to isoindolinone 3a in 80% de and a pure diastereoisomer was recovered after chromatography on silica gel (EtOAc/hexanes 3:7) and crystallization from hexanes/toluene. Reactions of substrates

• Scheme 5. Aldehyde 23 was first readily prepared via a Heck cross coupling reaction between 2-bromobenzaldehyde (22) and acrylamide 11f. Next, a Pinnick oxidation of the aldehyde 23 followed with a coupling reaction with chiral benzylamine 17 delivered the targeted benzamide 24 in good yield (65%). The

CF₃SO₂X (X = Na, Cl) as reagents for trifluoromethylation, trifluoromethylsulfenyl-, -sulfinyl- and -sulfonylation and chlorination. Part 2: Use of CF₃SO₂Cl

• Hélène Chachignon,
• Hélène Guyon and
• Dominique Cahard

Beilstein J. Org. Chem. 2017, 13, 2800–2818, doi:10.3762/bjoc.13.273

• most widely described type of reactions in which CF3SO2Cl and molecules carrying a C=C double bond are involved are actually cascade reactions that include a cyclisation or a group migration step. In this context, the acrylamide motif was a notably popular object of research, and served in several

CF₃SO₂X (X = Na, Cl) as reagents for trifluoromethylation, trifluoromethylsulfenyl-, -sulfinyl- and -sulfonylation. Part 1: Use of CF₃SO₂Na

• Hélène Guyon,
• Hélène Chachignon and
• Dominique Cahard

Beilstein J. Org. Chem. 2017, 13, 2764–2799, doi:10.3762/bjoc.13.272

• radical was generated from TBHP and Cu(n) via a SET process, which then, it reacted with CF3SO2Na to liberate CF3•. The subsequent addition of CF3• to the β-position of the C=C bond of the acrylamide gave the intermediate 48, which underwent an intramolecular radical annulation to produce the aryl radical

Detection of therapeutic radiation in three-dimensions

• John A. Adamovics

Beilstein J. Org. Chem. 2017, 13, 1325–1331, doi:10.3762/bjoc.13.129

• the polymerization of acrylamide with N,N’-methylenebisacrylamide and various monomers to yield a cloud like precipitate in the aqueous gel [13]. Due to the nature of their radical chemistry, polymer gel dosimeters have several limitations. They are susceptible to atmospheric oxygen inhibiting the

One-pot synthesis of block-copolyrotaxanes through controlled rotaxa-polymerization

• Jessica Hilschmann,
• Gerhard Wenz and
• Gergely Kali

Beilstein J. Org. Chem. 2017, 13, 1310–1315, doi:10.3762/bjoc.13.127

• acrylate and an acrylamide in the presence of methylated β-cyclodextrin was employed for the first time to synthesize block-copolyrotaxanes. RAFT polymerizations started from a symmetrical bifunctional trithiocarbonate and gave rise to triblock-copolymers where the outer polyacrylate/polyacrylamide blocks

• (hydroxymethyl)methyl]acrylamide (TRIS-AAm) or 2-hydroxyethyl methacrylate (HEMA), shown in Scheme 1. The role of these bulky comonomers was to prevent the unthreading of RAMEB rings from the polymeric axis during and after polymerization. The resulting statistical copolymers were clearly soluble in water thus

Highly reactive, liquid diacrylamides via synergistic combination of spatially arranged curing moieties

• Maximilian Maier,
• Magnus S. Schmidt,
• Markus Ringwald and
• Christoph P. Fik

Beilstein J. Org. Chem. 2017, 13, 372–383, doi:10.3762/bjoc.13.40

• synergistic combination of optimally arranged functional groups could be identified. The highest possible level of intramolecular synergism was found for low viscous N,N'-diacryloyl-N,N'-diallyl-1,4-but-2-enediamine. Keywords: acrylamide; allyl; cyclopolymerization; photopolymerization; spatial effect

• cyclopolymerization due to their adjacent double-bond functionalities [25][26][27]. The propagation reaction of these structures proceeds intramolecularly between acryl and allyl groups and intermolecularly (mostly) between polymer-radical and acrylamide groups. Cyclo- is preferred over linear polymerization due to

• has been realized. When allyl- and acrylamide functionalities were spatially adjacent, a “synergistic potential” beneficial in radical polymerization was expected (Scheme 1). Synthesis Six derivatives of highly functionalized crosslinkers 1–6 were synthesized as outlined in Scheme 2. We started from

Development of a continuous process for α-thio-β-chloroacrylamide synthesis with enhanced control of a cascade transformation

• Olga C. Dennehy,
• Valérie M. Y. Cacheux,
• Benjamin J. Deadman,
• Denis Lynch,
• Stuart G. Collins,
• Humphrey A. Moynihan and
• Anita R. Maguire

Beilstein J. Org. Chem. 2016, 12, 2511–2522, doi:10.3762/bjoc.12.246

• -chloroacrylamides; cascade reactions; flow chemistry; Introduction Since the efficient and highly stereoselective transformation of α-thioamides to the corresponding α-thio-β-chloroacrylamides derivatives was first reported [1][2], the considerable synthetic utility of these heavily functionalized acrylamide

• mechanism (Scheme 7) involves a complex cascade which also gives rise to several known impurities, including acrylamide 4, dichloride 5, trichloride 6 and dichloroacrylamide 7. In the optimized batch synthesis of α-thio-β-chloroacrylamide Z-3 from the corresponding α-thioamide 2, N-chlorosuccinimide (NCS

• outcome (entries 1 and 2, Table 2). Indeed, the conversion of starting material 2 to acrylamide 4 was found to be closely comparable, indicating almost identical reaction progress, given the instability of dichloride 5, which easily converts to the final product Z-3. Increasing the amounts of NCS used was

Radical polymerization by a supramolecular catalyst: cyclodextrin with a RAFT reagent

• Kohei Koyanagi,
• Yoshinori Takashima,
• Takashi Nakamura,
• Hiroyasu Yamaguchi and
• Akira Harada

Beilstein J. Org. Chem. 2016, 12, 2495–2502, doi:10.3762/bjoc.12.244

• β-CD cavity of β-CD-CTA was capped by the CTA unit, inhibiting the molecular recognition property. Crystal structure of the α-CD-DMA and β-CD-DMA complexes We chose N,N-dimethylacrylamide (DMA), acrylic acid (AA), and acrylamide (AAm) as water-soluble vinyl monomers for radical polymerization. Prior

Rh-Catalyzed reductive Mannich-type reaction and its application towards the synthesis of (±)-ezetimibe

• Motoyuki Isoda,
• Kazuyuki Sato,
• Yurika Kunugi,
• Satsuki Tokonishi,
• Atsushi Tarui,
• Masaaki Omote,
• Hideki Minami and
• Akira Ando

Beilstein J. Org. Chem. 2016, 12, 1608–1615, doi:10.3762/bjoc.12.157

• imine at the α-position (Table 1, entry 9). By using [RhCl(cod)]2, the α,β-unsaturated lactone was also converted to the product with a small improvement in the yield (Table 1, entry 11). Acrylamide 2i also gave the corresponding β-aminoamide 4Ai in a low yield (Table 1, entry 12). In the reaction using

Conjugate addition–enantioselective protonation reactions

• James P. Phelan and
• Jonathan A. Ellman

Beilstein J. Org. Chem. 2016, 12, 1203–1228, doi:10.3762/bjoc.12.116

• N-benzyloxycarbonyl acrylamide by 80 activates it for conjugate addition of the amine to generate chiral enolate 82. Enantioselective protonation of chiral enolate 82 by a second equivalent of amine salt liberates the product as the triflate salt and regenerates 80 and the free amine. Building upon

A cross-metathesis approach to novel pantothenamide derivatives

• Jinming Guan,
• Matthew Hachey,
• Lekha Puri,
• Vanessa Howieson,
• Kevin J. Saliba and
• Karine Auclair

Beilstein J. Org. Chem. 2016, 12, 963–968, doi:10.3762/bjoc.12.95

• low yields might be explained by homodimerization of the acrylamide moiety. 2-Vinylpyridine (10b) reacted in even lower yields (14%), as expected based on the known deactivation of catalyst 3 in the presence of pyridinyl ligands [22]. A previous work by Grubbs and co-workers has demonstrated that

Supramolecular polymer assembly in aqueous solution arising from cyclodextrin host–guest complexation

• Jie Wang,
• Zhiqiang Qiu,
• Yiming Wang,
• Li Li,
• Xuhong Guo,
• Duc-Truc Pham,
• Stephen F. Lincoln and
• Robert K. Prud’homme

Beilstein J. Org. Chem. 2016, 12, 50–72, doi:10.3762/bjoc.12.7

• -dimethylacrylamide (DMAA) or N-isopropylacrylamine (NIPAAM) with 1-adamantylacrylamide, and of the copolymer of NIPAAM with 6-acryloylaminohexanoic acid in which the ratio of the acrylamide units to adamantyl subunits is 20:1 have been reported by Ritter et al. [102]. They find that the viscosity of 50 g/L aqueous

• water, cyclodextrins have attracted attention as components of self-healing materials. Thus, Harada et al. constructed self-healing supramolecular hydrogels from poly(acrylamide) substituted with both cyclodextrins and aliphatic substituents. This is exemplified by one such system in which the radical

• copolymerization of aqueous acrylamide, acrylamide substituted β-CD and N-adamantyl-acrylamide gives a β-CD- and adamantyl-substituted poly(acrylamide) which forms a hydrogel as shown in Figure 21 [108]. When a portion of the hydrogel is cut in two and both halves are brought back into close contact, the cut

Preparative semiconductor photoredox catalysis: An emerging theme in organic synthesis

• David W. Manley and
• John C. Walton

Beilstein J. Org. Chem. 2015, 11, 1570–1582, doi:10.3762/bjoc.11.173

• with optically pure amino acids probably because the released radicals were planar, or close to planar. Radical additions took place to other alkene substrates such as acrylamide but extensive polymerization was observed with methyl methacrylate. The phenoxyacetic acid/acrylamide reaction was chosen to

Radical-mediated dehydrative preparation of cyclic imides using (NH₄)₂S₂O₈–DMSO: application to the synthesis of vernakalant

• Dnyaneshwar N. Garad,
• Subhash D. Tanpure and
• Santosh B. Mhaske

Beilstein J. Org. Chem. 2015, 11, 1008–1016, doi:10.3762/bjoc.11.113

• synthesis of imides from the combination of aliphatic amines and unsaturated anhydrides. Plausibly, the intermediate amic acid in these cases may be prone to decarboxylation [57] and radical polymerization similar to the acrylamide polymerization using APS as a radical initiator [55]. Encouraged by this

Peptide–polymer ligands for a tandem WW-domain, an adaptive multivalent protein–protein interaction: lessons on the thermodynamic fitness of flexible ligands

• Katharina Koschek,
• Vedat Durmaz,
• Oxana Krylova,
• Marek Wieczorek,
• Shilpi Gupta,
• Martin Richter,
• Alexander Bujotzek,
• Christina Fischer,
• Rainer Haag,
• Christian Freund,
• Marcus Weber and
• Jörg Rademann

Beilstein J. Org. Chem. 2015, 11, 837–847, doi:10.3762/bjoc.11.93

• with an average MW of either 10 kDa (for Dex-1 and Dex-2) or 50 kDa (for Dex-3), both with a polydispersity index of 1.5. Under basic conditions the linear polysaccharide was alkylated with acrylamide selectively in the 2-positions of the sugars. The resulting 2-O-carboxyethyl dextran (2-O-CE-dextran

Synthesis of tripodal catecholates and their immobilization on zinc oxide nanoparticles

• Franziska Klitsche,
• Julian Ramcke,
• Julia Migenda,
• Andreas Hensel,
• Tobias Vossmeyer,
• Horst Weller,
• Silvia Gross and
• Wolfgang Maison

Beilstein J. Org. Chem. 2015, 11, 678–686, doi:10.3762/bjoc.11.77

• chloride to give acrylamide 4. Treatment of 4 with dimethylamine and excess KOH leads to the nucleophilic addition of the amine and saponification of the methyl esters in one step to give the free acid 5 after acidic work-up. Subsequent coupling of 5 to dopamine acetonide 6 with EDC and HOBt gave the

• an effector was prepared. This triscatecholate might be useful for the construction of diamandoid hydrophobic coatings [44] or for the reversible attachment of cyclodextrins to NPs by the formation of cyclodextrin/adamantane inclusion complexes [45]. Alternatively, acrylamide 4 and bromide 12 [42

Morita–Baylis–Hillman reaction of acrylamide with isatin derivatives

• Radhey M. Singh,
• Kishor Chandra Bharadwaj and
• Dharmendra Kumar Tiwari

Beilstein J. Org. Chem. 2014, 10, 2975–2980, doi:10.3762/bjoc.10.315

• Abstract The Morita–Baylis–Hillman reaction of acrylamide, as an activated alkene, has seen little development due to its low reactivity. We have developed the reaction using isatin derivatives with acrylamide, DABCO as a promoter and phenol as an additive in acetonitrile. The corresponding aza version

• with acrylate and acrylonitrile has also been developed resulting in high product yields. Keywords: acrylamide; isatin; ketimine; Morita–Baylis–Hillman; phenol; Introduction The Morita–Baylis–Hillman (MBH) reaction is an important carbon–carbon bond-forming reaction [1][2][3]. It involves the

• , the acryl system shows differences in reactivity upon slight structural modifications. In such a system, the enone and acrylonitrile are more reactive, while with the acrylate reaction is relatively slow. Furthermore, there is a decrease of reactivity with acrylamide due to the reduced Michael

End group functionalization of poly(ethylene glycol) with phenolphthalein: towards star-shaped polymers based on supramolecular interactions

• Carolin Fleischmann,
• Hendrik Wöhlk and
• Helmut Ritter

Beilstein J. Org. Chem. 2014, 10, 2263–2269, doi:10.3762/bjoc.10.235

• phenolphthalein (see Scheme 1). In a first step, the monofunctional phenolphthalein-monomer N-(2-hydroxy-5-(1-(4-hydroxyphenyl)-3-oxo-1,3-dihydroisobenzofuran-1-yl)benzyl)acrylamide (PP-AAm) was synthesized following a protocol we developed in a previous study [46]. Afterwards, the corresponding amine derivative

The regioselective synthesis of spirooxindolo pyrrolidines and pyrrolizidines via three-component reactions of acrylamides and aroylacrylic acids with isatins and α-amino acids

• Tatyana L. Pavlovskaya,
• Fedor G. Yaremenko,
• Victoria V. Lipson,
• Svetlana V. Shishkina,
• Oleg V. Shishkin,
• Vladimir I. Musatov and
• Alexander S. Karpenko

Beilstein J. Org. Chem. 2014, 10, 117–126, doi:10.3762/bjoc.10.8

• azomethine ylide, which regioselectively adds to the C=C bond of acrylamide or aroylacrylic acid. Since the stereochemistry of the cycloadducts 4a and 6a was clarified by a single-crystal X-ray analysis, the structures of the reacting systems – the azomethine ylide and dipolarophiles (acrylamide and

• verified by calculations of vibrational frequencies within the harmonic approximation, using analytical second derivatives at the same level of theory. All stationary points possess zero imaginary frequencies. It was found that the acrylamide conformer I was more stable than conformer II by 1.24 kcal/mol

• the most reactive sites of the reagents. The reaction proceeds regioselectively with the addition of the most nucleophilic methylene group carbon of the azomethine ylide to the most electrophilic sites of the acrylamide and benzoylacrylic acid, which affords only one stereoisomer of cycloadducts 4 and

Polymeric redox-responsive delivery systems bearing ammonium salts cross-linked via disulfides

• Christian Dollendorf,
• Martin Hetzer and
• Helmut Ritter

Beilstein J. Org. Chem. 2013, 9, 1652–1662, doi:10.3762/bjoc.9.189

• of DNA encapsulation used in anti-cancer treatment [16][17][18][19][20][21][22][23]. Further examples for polymeric networks based on poly(ethylenimine) (PEI) or poly(diethyl acrylamide) (PDEA) can be found in the literature [24][25][26]. Disulfide bonds are generally stable in human blood

A construction of 4,4-spirocyclic γ-lactams by tandem radical cyclization with carbon monoxide

• Mitsuhiro Ueda,
• Yoshitaka Uenoyama,
• Nozomi Terasoma,
• Shoko Doi,
• Shoji Kobayashi,
• Ilhyong Ryu and
• John A. Murphy

Beilstein J. Org. Chem. 2013, 9, 1340–1345, doi:10.3762/bjoc.9.151

• cyclization due to the longer C–S bonds. We then tried to extend the tandem spirocyclization approach to obtain 4,4-spirocyclic oxindole γ-lactam and tested two substrates, 2-(azidomethyl)-N-benzyl-N-(2-iodophenyl)acrylamide (1f) and the nitrogen-unprotected analogue 1g. The reaction of 1f was smooth to give

• -iodophenyl)acrylamide (1f) (150.0 mg, 0.36 mmol), AIBN (2,2’-azobisisobutyronitrile, 17.7 mg, 0.11 mmol), TTMSS ([tris(trimethylsilyl)silane], 178.3 mg, 0.72 mmol) and THF (17.9 mL; 0.02 M) were placed in a 50 mL stainless steel autoclave. The autoclave was closed, purged three times with CO, pressurized