Spectroelectrochemical studies on the effect of cations in the alkaline glycerol oxidation reaction over carbon nanotube-supported Pd nanoparticles

• Dennis Hiltrop,
• Steffen Cychy,
• Karina Elumeeva,
• Wolfgang Schuhmann and
• Martin Muhler

Beilstein J. Org. Chem. 2018, 14, 1428–1435, doi:10.3762/bjoc.14.120

• from starch, sugar or oils and fats [2][3]. The transesterification of oils and fats produces glycerol as a byproduct, which requires further processing to reduce the costs of biofuels [4]. The comparably high energy density of glycerol of 5965 Wh L−1 assuming its total oxidation to CO2 suggests its

Design and biological characterization of novel cell-penetrating peptides preferentially targeting cell nuclei and subnuclear regions

• Anja Gronewold,
• Mareike Horn and
• Ines Neundorf

Beilstein J. Org. Chem. 2018, 14, 1378–1388, doi:10.3762/bjoc.14.116

• the molar ellipticity at 222 nm and 207 nm was used to confirm an α-helical structure of peptides [25]. Cell culturing All cell lines were grown in sterile culture dishes in a CO2 incubator (5% CO2) at 37 °C. HeLa and MCF-7 were grown in RPMI-1640 medium containing 10% fetal bovine serum (FBS) and 4

A three-armed cryptand with triazine and pyridine units: synthesis, structure and complexation with polycyclic aromatic compounds

• Claudia Lar,
• Adrian Woiczechowski-Pop,
• Attila Bende,
• Ioana Georgeta Grosu,
• Natalia Miklášová,
• Elena Bogdan,
• Niculina Daniela Hădade,
• Anamaria Terec and
• Ion Grosu

Beilstein J. Org. Chem. 2018, 14, 1370–1377, doi:10.3762/bjoc.14.115

• [32] revealed its selective absorption ability for N2 and CO2 in the solid state. The low complexation ability of cryptand 1 in solution for aromatic guests is due to the unfavorable conformation of the 1,3,5-triphenylbenzene central units in which the peripheral aromatic rings are twisted with

[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

• absence of light. Depending on the temperature, a new reaction pathway involving benzylic group migration, CO2 extrusion and final cycloaddition was proposed (Scheme 4). Kinetics and mechanism of thermal cycloaddition The kinetics and reaction mechanism of the thermal cycloaddition between 4-methyl-3

• bicyclic intermediate via a concerted [3 + 2]-cycloaddition followed by its very fast decomposition (extrusion of CO2) via a retro-Diels–Alder [4 + 2]-cycloaddition. The almost spontaneous extrusion of CO2 is caused by an energetically favorable aromatization occurring in this step leading to the formation

• its slow decomposition to pyrazole and CO2. Such ambiguous substitution effects are therefore worthy of further investigations. Photochemical reaction of sydnones with symmetrical alkynes In 1966 Krauch et al. [59] dealt with irradiation (using a high-pressure Hg lamp) of benzene or dioxane solutions

An overview of recent advances in duplex DNA recognition by small molecules

• Sayantan Bhaduri,
• Nihar Ranjan and
• Dev P. Arya

Beilstein J. Org. Chem. 2018, 14, 1051–1086, doi:10.3762/bjoc.14.93

Mechanochemistry of nucleosides, nucleotides and related materials

• Olga Eguaogie,
• Joseph S. Vyle,
• Patrick F. Conlon,
• Manuela A. Gîlea and
• Yipei Liang

Beilstein J. Org. Chem. 2018, 14, 955–970, doi:10.3762/bjoc.14.81

• derivatives, Sikchi and Hultin contrived an attritor-type mill (Figure 1c) to facilitate the use of neat reagents and vent CO2 (closed vessels were reported to break) [19]. Efficient gram-scale Boc protection of amine and carboxylic acid functions was thereby effected (Scheme 3). This chemistry was further

Phosphodiester models for cleavage of nucleic acids

• Satu Mikkola,
• Tuomas Lönnberg and
• Harri Lönnberg

Beilstein J. Org. Chem. 2018, 14, 803–837, doi:10.3762/bjoc.14.68

Synthesis and in vitro biochemical evaluation of oxime bond-linked daunorubicin–GnRH-III conjugates developed for targeted drug delivery

• Sabine Schuster,
• Beáta Biri-Kovács,
• Bálint Szeder,
• Viktor Farkas,
• László Buday,
• Zsuzsanna Szabó,
• Gábor Halmos and
• Gábor Mező

Beilstein J. Org. Chem. 2018, 14, 756–771, doi:10.3762/bjoc.14.64

• plastic culture dishes at 37 °C with a humidified atmosphere containing 5% CO2/95% air. Stability of GnRH-III bioconjugates in cell culture medium The GnRH-III bioconjugates were dissolved in water to a concentration of 2.5 mg/mL followed by the dilution with serum-free cell culture medium (final

Latest development in the synthesis of ursodeoxycholic acid (UDCA): a critical review

• Fabio Tonin and
• Isabel W. C. E. Arends

Beilstein J. Org. Chem. 2018, 14, 470–483, doi:10.3762/bjoc.14.33

• most used enzymes for the cofactor regeneration are glucose dehydrogenase (glucose to glucuronic acid), lactate dehydrogenase (pyruvate to lactate), glutamate dehydrogenase (α-ketoglutarate to glutamate) and formate dehydrogenase (formate to CO2). In particular, the last enzyme is interesting because

• formate is cheap and, because of the gaseous nature of CO2 as product, the equilibrium of the reaction is entropically favoured. Pedrini et al. in 2006 [33] reported the successful epimerization of CDCA to UDCA using a redox-neutral cascade reaction, with two NAD+-dependent dehydrogenases. In this way the

Synthesis of fluoro-functionalized diaryl-λ³-iodonium salts and their cytotoxicity against human lymphoma U937 cells

• Prajwalita Das,
• Etsuko Tokunaga,
• Hidehiko Akiyama,
• Hiroki Doi,
• Norimichi Saito and
• Norio Shibata

Beilstein J. Org. Chem. 2018, 14, 364–372, doi:10.3762/bjoc.14.24

• × 105 cells/well) and incubated at 37 °C for 24 h. MTT reagent (10 μL) was added to each well. After mixing gently, the cells were incubated for 3 h at 37 °C in a CO2 incubator. The culture medium was aspirated and the crystal-dissolving solution (100 μL) was added to each well and mixed. Finally, the

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

• DMF decomposed into Cu2+, difluorocarbene and fluoride with the release of SO2 and CO2. Then, difluorocarbene and fluoride combined into a CF3 species in the presence of Cu2+ and Cu. In contrast with the majority of previously reported copper-mediated trifluoromethylation reactions of haloarenes

The photodecarboxylative addition of carboxylates to phthalimides as a key-step in the synthesis of biologically active 3-arylmethylene-2,3-dihydro-1H-isoindolin-1-ones

• Ommid Anamimoghadam,
• Saira Mumtaz,
• Anke Nietsch,
• Gaetano Saya,
• Cherie A. Motti,
• Jun Wang,
• Peter C. Junk,
• Ashfaq Mahmood Qureshi and
• Michael Oelgemöller

Beilstein J. Org. Chem. 2017, 13, 2833–2841, doi:10.3762/bjoc.13.275

• excess amounts to suppress competing ‘simple’ decarboxylation (-CO2− ↔ -H exchange) reactions to the corresponding toluene derivatives [25]. Following the established protocol and utilizing a 1:1 acetone/water mixture as reaction medium [27][30], irradiations with UVB light (300 ± 30 nm) for 4 hours

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

Pyrene–nucleobase conjugates: synthesis, oligonucleotide binding and confocal bioimaging studies

• Artur Jabłoński,
• Yannic Fritz,
• Hans-Achim Wagenknecht,
• Rafał Czerwieniec,
• Tytus Bernaś,
• Damian Trzybiński,
• Krzysztof Woźniak and
• Konrad Kowalski

Beilstein J. Org. Chem. 2017, 13, 2521–2534, doi:10.3762/bjoc.13.249

• cells were cultured for 48 h after seeding in Petri dishes with glass bottom (MaTek), reaching approximately 50% confluency. The cells were grown in Dulbeco’s minimal essential medium (DMEM) with 5% FCS, at 5% CO2 and 37 °C. The same medium was used to perform all microscopy experiments. Directly before

Hydrolysis, polarity, and conformational impact of C-terminal partially fluorinated ethyl esters in peptide models

• Vladimir Kubyshkin and
• Nediljko Budisa

Beilstein J. Org. Chem. 2017, 13, 2442–2457, doi:10.3762/bjoc.13.241

• , 2.5 Hz, α-CH), 3.73 (s, OCH3), 3.47 (ddd, JHH = 11.6, 8.5, 3.5 Hz, δ-CH), 3.41 (dt, JHH = 11.4, 8.4 Hz, δ-CH), 2.27 and 2.15 (two m, β-CH2), 1.93 (s, CH3C=O), 1.89 and 1.79 (two m, γ-CH2); 13C{1H} NMR (D2O, 126 MHz) δ s-trans, 175.0 (s, CO2), 173.0 (s, N-C=O), 59.0 (s, α-CH), 52.9 (s, OCH3), 48.4 (s

• , δ-CH2), 29.2 (s, β-CH2), 24.2 (s, γ-CH2), 21.2 (s, CH3); s-cis, 174.6 (s, CO2), 173.4 (s, N-C=O), 60.7 (s, α-CH), 53.2 (s, OCH3), 46.6 (s, δ-CH2), 30.6 (s, β-CH2), 22.3 (s, γ-CH2), 21.2 (s, CH3); HRMS (ESI-orbitrap): [M + H]+ calcd for C8H14NO3, 172.0968; found, 172.0968; [α]D25 −83 (c 2.0, CHCl3

• ), 4.20 (q, JHH = 7.2 Hz, OCH2), 3.47 (ddd, JHH = 11.5, 8.7, 3.7 Hz, δ-CH), 3.41 (dt, JHH = 11.5, 8.3 Hz, δ-CH), 2.28 and 2.15 (two m, β-CH2), 1.93 (s, CH3C=O), 1.90 and 1.80 (two m, γ-CH2); 13C{1H} NMR (D2O, 176 MHz) δ s-trans, 174.7 (s, CO2), 173.0 (s, N-C=O), 62.6 (s, OCH2), 59.3 (s, α-CH), 48.5 (s, δ

Synthesis and application of trifluoroethoxy-substituted phthalocyanines and subphthalocyanines

• Satoru Mori and
• Norio Shibata

Beilstein J. Org. Chem. 2017, 13, 2273–2296, doi:10.3762/bjoc.13.224

• phthalocyanines. TFEO-Pc is soluble not only in general organic solvents but also in liquid carbon dioxide (CO2) and supercritical CO2 [55]. These forms of CO2 have attracted attention as solvents which do not discharge volatile organic compounds (VOCs), and are expected to replace organic solvents as a

• countermeasure to VOC emissions [56][57][58]. Phthalocyanines that show solubility in CO2 are useful for industrial applications because they can be applied without using an organic solvent [59][60]. The plus and minus signs shown in Table 1 express solubility, where (+) means readily soluble, (−) means

• sparingly soluble, (++) means very high solubility, and (±) means moderate solubility. After conducting solubility studies on various phthalocyanines, only phthalocyanine in which all positions were substituted with trifluoroethoxy groups showed high solubility in both liquid CO2 and supercritical CO2. On

A mechanochemical approach to access the proline–proline diketopiperazine framework

• Nicolas Pétry,
• Hafid Benakki,
• Eric Clot,
• Pascal Retailleau,
• Farhate Guenoun,
• Fatima Asserar,
• Chakib Sekkat,
• Thomas-Xavier Métro,
• Jean Martinez and
• Frédéric Lamaty

Beilstein J. Org. Chem. 2017, 13, 2169–2178, doi:10.3762/bjoc.13.217

• it would avoid a potential pressure build-up (release of CO2) which could occur with NaHCO3. Noteworthy, no epimerization could be detected by NMR or HPLC analyses. Both peptides 7 and 8 were then deprotected and cyclized into the corresponding diketopiperazine 9. Palladium-catalyzed hydrogenolysis

Novel approach to hydroxy-group-containing porous organic polymers from bisphenol A

• Tao Wang,
• Yan-Chao Zhao,
• Li-Min Zhang,
• Yi Cui,
• Chang-Shan Zhang and
• Bao-Hang Han

Beilstein J. Org. Chem. 2017, 13, 2131–2137, doi:10.3762/bjoc.13.211

• crucial factor that influences the amount of adsorbed CO2, whereas the uptake capacity is more depended on porosity characteristic such as pore size in the networks [36][37]. Specially, the smallest pores contribute most to the CO2 uptake at low pressure [36]. Hence, PPOP-3 with a smaller pore size

• located at 0.68 nm that is different from the other two polymers in Figure 3b is probably the best candidate for CO2 capture. The high carbon dioxide uptake capacity for PPOPs may correspond to the large amount of the hydroxy groups in the PPOPs through the formation of O=C=O(δ–)…H(δ+)–O hydrogen bonds

• Information File 1, Figure S8). The typical heats of absorption Qst for the PPOPs are measured in the range of about 21.6–24.3 kJ mol−1 (Figure 5), which are in accordance with the report data [40], indicating that the adsorption of CO2 is mainly physical adsorption. Unusually, PPOP-2 and PPOP-3 show an

Block copolymers from ionic liquids for the preparation of thin carbonaceous shells

• Sadaf Hanif,
• Bernd Oschmann,
• Dmitri Spetter,
• Muhammad Nawaz Tahir,
• Wolfgang Tremel and
• Rudolf Zentel

Beilstein J. Org. Chem. 2017, 13, 1693–1701, doi:10.3762/bjoc.13.163

• are applied as catalytic membranes, thermotropic liquid crystals [12], polymer electrolytes, ionic conductive materials, CO2 absorbing materials, microwave absorbing materials and porous materials [4]. Most of these polymers were synthesized by free radical polymerization. There are just few reports

Oxidative dehydrogenation of C–C and C–N bonds: A convenient approach to access diverse (dihydro)heteroaromatic compounds

• Santanu Hati,
• Ulrike Holzgrabe and
• Subhabrata Sen

Beilstein J. Org. Chem. 2017, 13, 1670–1692, doi:10.3762/bjoc.13.162

• phthalimide-N-oxyl radical (PINO) via transfer of hydrogen from NHPI to O2. Co2+-assisted this step by associating with oxygen to generate a Co3+–oxygen complex. It then abstracts the hydrogen from NHPI. Next, PINO abstracted a hydrogen from the DHP produced to generate radical X which aromatizes via hydrogen

Synthesis and metal binding properties of N-alkylcarboxyspiropyrans

• Alexis Perry and
• Christina J. Kousseff

Beilstein J. Org. Chem. 2017, 13, 1542–1550, doi:10.3762/bjoc.13.154

• metals was in the order Zn2+ > Mg2+ > Co2+ > Ni2+. Binding to Ni2+ was considerably less effective than for other divalent metal cations and this was particularly pronounced for non-carboxylate 9, wherein 9–Ni2+ complexation did not exceed background [merocyanine]. Merocyanine complexation of Cu2+ was

• into the merocyanine structure did increase the affinity for Zn2+, Mg2+ and Co2+ over that seen in the non-carboxylate control compound 9. It is apparent from these data that the length of the carboxylate tether can also affect the spiropyran–merocyanine equilibrium in the absence of metal cations

Sustainable synthesis of 3-substituted phthalides via a catalytic one-pot cascade strategy from 2-formylbenzoic acid with β-keto acids in glycerol

• Lina Jia and
• Fuzhong Han

Beilstein J. Org. Chem. 2017, 13, 1425–1429, doi:10.3762/bjoc.13.139

• straightforward method for the preparation of several biologically active compounds of medicinal and agrochemical interest [23][24][25][26][27][28][29][30]. Notably, the decarboxylative reaction of β-keto acids provides a traceless means of activation with CO2 as the only byproduct. On the other hand, glycerol

Biomimetic molecular design tools that learn, evolve, and adapt

• David A Winkler

Beilstein J. Org. Chem. 2017, 13, 1288–1302, doi:10.3762/bjoc.13.125

• of porous materials for hydrogen storage and CO2 capture and reduction Porous materials, such as metal organic frameworks (MOFs), covalent organic frameworks (COFs) and zeolitic imidazolate frameworks (ZIFs) are attracting much interest because of the large numbers of bespoke materials that can be

• designed and synthesized using these self-assembly paradigms. They are being developed to tackle two major and interrelated environmental challenges facing the planet, the rise in CO2 levels in the atmosphere due to burning of fossil fuels, and the storage of hydrogen for zero carbon emission transport

Sugar-based micro/mesoporous hypercross-linked polymers with in situ embedded silver nanoparticles for catalytic reduction

• Qing Yin,
• Qi Chen,
• Li-Can Lu and
• Bao-Hang Han

Beilstein J. Org. Chem. 2017, 13, 1212–1221, doi:10.3762/bjoc.13.120

• volume, and pore size, are calculated based on the corresponding isotherms and listed in Table 1. Such HCPs with a high SSA and micro/mesopore distribution inspired us to explore their gas uptake capacity. The CO2 adsorption isotherms of the three polymers at 1.0 bar and 273 K are shown in Figure S5

• (Supporting Information File 1). The polymer SugPOP-1 having a higher SSA and pore volume also exhibits a higher CO2 adsorption capacity (14.4 wt %) than SugPOP-2 (12.8 wt %) and SugPOP-3 (10.5 wt %). Additionally, the hydroxy-group-bearing SugPOP-1 can form hydrogen bonds with carbon dioxide, which may

• increase the affinity to carbon dioxide. Compared with the reported polymer Glc-3 [17] (prepared using the same monomer as for SugPOP-1 and with a similar method), the polymer SugPOP-1 also possesses a higher CO2 adsorption capacity due to its higher porosity. Compared with a class of microporous HCPs

Automating multistep flow synthesis: approach and challenges in integrating chemistry, machines and logic

• Chinmay A. Shukla and
• Amol A. Kulkarni

Beilstein J. Org. Chem. 2017, 13, 960–987, doi:10.3762/bjoc.13.97