Synthesis of aliphatic nitriles from cyclobutanone oxime mediated by sulfuryl fluoride (SO₂F₂)

• Xian-Lin Chen and
• Hua-Li Qin

Beilstein J. Org. Chem. 2023, 19, 901–908, doi:10.3762/bjoc.19.68

• cyclobutanone oximes. Substrate scope of δ-olefin-containing aliphatic nitriles. Reaction conditions: A mixture of cyclobutanone oxime derivative 1 (3.0 mmol, 3.0 equiv), alkene 2 (1.0 mmol, 1.0 equiv), Cu2O (1.0 mmol, 1.0 equiv) and potassium acetate (10.0 mmol, 10.0 equiv) in extra dry dioxane or DMSO (0.1 M

Pyridine C(sp²)–H bond functionalization under transition-metal and rare earth metal catalysis

• Haritha Sindhe,
• Malladi Mounika Reddy,
• Karthikeyan Rajkumar,
• Akshay Kamble,
• Amardeep Singh,
• Anand Kumar and
• Satyasheel Sharma

Beilstein J. Org. Chem. 2023, 19, 820–863, doi:10.3762/bjoc.19.62

Eschenmoser coupling reactions starting from primary thioamides. When do they work and when not?

• Lukáš Marek,
• Jiří Váňa,
• Jan Svoboda and
• Jiří Hanusek

Beilstein J. Org. Chem. 2023, 19, 808–819, doi:10.3762/bjoc.19.61

• 70–95%). The presence of a base and the type of solvent seems to be an important factor for the reaction course. In toluene, ionic liquid or in refluxing ethanol without a base [16][19][20] or in the presence of weakly basic pyridine [17][18][21] (pKa = 5.23 in water, 3.4 in DMSO, 3.3 in DMF, and

• . recommended [24] a polar aprotic solvent such as DMSO that facilitates the formation of both α-thioiminium salt (III) as well as Eschenmoser contraction involving the attack of the exposed carbanion towards the imine/iminium group (V). Based on our previous experience [3][4] we favor dimethylformamide (DMF

• solutions (DMSO-d6, MeOD-d4, D2O), it was impossible to measure its NMR spectra and the only characterization involves MALDI–MS, IR, and melting point. The salt 6a was then treated in various solvents with or without additive (thiophile, base/acid) to give diverse products of cyclization (8a or 8a-Me), ECR

Non-peptide compounds from Kronopolites svenhedini (Verhoeff) and their antitumor and iNOS inhibitory activities

• Yuan-Nan Yuan,
• Jin-Qiang Li,
• Hong-Bin Fang,
• Shao-Jun Xing,
• Yong-Ming Yan and
• Yong-Xian Cheng

Beilstein J. Org. Chem. 2023, 19, 789–799, doi:10.3762/bjoc.19.59

• culture, cells were pretreated with compounds at a 20 μM concentration or DMSO for 48 h, with gemcitabine as a positive reference drug. Subsequently, Cell Count Kit-8 (CCK-8, MCE, USA) was added to each well at a 10 μL concentration for 2 h. The absorbance at 450 nm was measured using a microplate reader

• cytometry (BD, USA). CD8+ T cells and Panc02-h7-GP-GFP cells were co-cultured with the corresponding concentrations of compounds or DMSO for 18 h. Fluorescence intensity was measured using a microplate reader (emission at 476 nm, excitation at 514 nm). Anti-inflammatory assay RAW264.7 (a mouse macrophage

• /mL under the same incubation conditions. Following overnight incubation, the cells were treated with the corresponding concentration of the compound or DMSO for 24 h. CCK-8 (Beyotime, China) solution was added and incubated for 1 h. The absorbance of the solution in the 96-well plate was measured

Synthesis of substituted 8H-benzo[h]pyrano[2,3-f]quinazolin-8-ones via photochemical 6π-electrocyclization of pyrimidines containing an allomaltol fragment

• Constantine V. Milyutin,
• Andrey N. Komogortsev,
• Boris V. Lichitsky,
• Mikhail E. Minyaev and
• Valeriya G. Melekhina

Beilstein J. Org. Chem. 2023, 19, 778–788, doi:10.3762/bjoc.19.58

• the model compound 10a in DMSO-d6 solution using 1H NMR monitoring (Figure 1). Thus, the NMR spectrum recorded after UV irradiation (365 nm) for 24 h contained signals of protons of two products along with signals of the starting pyrimidine 10a (Figure 1B). The complete conversion of the starting

• DMSO-d6 solution. The crystal structure of compound 11a (one of two polymorph modifications; p = 50%), CCDC 2248033. One of crystallographically unique molecules of 11g (p = 50%), CCDC 2248035. Photochemical behavior of terarylenes containing an allomaltol fragment. Synthesis of starting compounds 9

Synthesis of imidazo[1,2-a]pyridine-containing peptidomimetics by tandem of Groebke–Blackburn–Bienaymé and Ugi reactions

• Oleksandr V. Kolomiiets,
• Alexander V. Tsygankov,
• Maryna N. Kornet,
• Aleksander A. Brazhko,
• Vladimir I. Musatov and
• Valentyn A. Chebanov

Beilstein J. Org. Chem. 2023, 19, 727–735, doi:10.3762/bjoc.19.53

• -chlorobenzaldehyde (5b), 4-methoxyaniline (6a) and tert-butyl isocyanide (3a). It should be especially noted that the solubility of compound 8a is very low (soluble in DMSO and N-methyl-2-pyrrolidone (NMP), slightly soluble in methanol, 1- and 2-propanol, acetone, DMF and insoluble in water, ethanol, acetonitrile

• use DMSO, DMF and NMP as solvents for this Ugi treatment. However, we found that the application of the solvent systems based on DMF and DMSO described in the literature [35][36] did not lead to the target compound 9a (Scheme 5, Table 2). Stirring at elevated temperatures or reaction in NMP also

Synthesis, structure, and properties of switchable cross-conjugated 1,4-diaryl-1,3-butadiynes based on 1,8-bis(dimethylamino)naphthalene

• Semyon V. Tsybulin,
• Ekaterina A. Filatova,
• Alexander F. Pozharskii,
• Valery A. Ozeryanskii and
• Anna V. Gulevskaya

Beilstein J. Org. Chem. 2023, 19, 674–686, doi:10.3762/bjoc.19.49

• Supporting Information, File 1, Figure S60). The further alkynylation of compounds 7a–e was carried out using trimethylsilylacetylene and the Pd(PPh3)2Cl2/CuI/Et3N/DMSO catalytic system giving rise to dialkynyl derivatives 10a–e in high yields (Scheme 2). Column chromatography of trimethylsilyl derivatives

• aryl fragment, the less intense the long-wavelength maximum. Conjugation between the aryl substituent and the DMAN fragment in salts 11 is indirectly supported by the fact that the basicity of monomer 6b with the donor methoxy group (pKa = 8.2, measured in DMSO by the 1H NMR transprotonation approach

Cassane diterpenoids with α-glucosidase inhibitory activity from the fruits of Pterolobium macropterum

• Sarot Cheenpracha,
• Ratchanaporn Chokchaisiri,
• Lucksagoon Ganranoo,
• Sareeya Bureekaew,
• Thunwadee Limtharakul and
• Surat Laphookhieo

Beilstein J. Org. Chem. 2023, 19, 658–665, doi:10.3762/bjoc.19.47

• according to experimental literature with slight modification [20]. α-Glucosidase (0.05 U/mL) and substrate, p-nitrophenyl-α-ᴅ-glucopyronoside (p-NPG) (1 mM) were dissolved in 0.1 M sodium phosphate buffer (pH 6.9). Fifty μL of sample (1 mg/mL in 10% DMSO) and 50 μL of α-glucosidase were preincubated at 37

Nucleophile-induced ring contraction in pyrrolo[2,1-c][1,4]benzothiazines: access to pyrrolo[2,1-b][1,3]benzothiazoles

• Ekaterina A. Lystsova,
• Maksim V. Dmitriev,
• Andrey N. Maslivets and
• Ekaterina E. Khramtsova

Beilstein J. Org. Chem. 2023, 19, 646–657, doi:10.3762/bjoc.19.46

• (toluene, acetonitrile, DMSO-d6) at room temperature, or when these solutions were slightly heated, the compounds 5a,b,e dissociated to form APBTTs 1 (the solutions got violet color, characteristic of compounds 1) (Scheme 10). In the presence of water (including the atmospheric moisture), hydration

Phenanthridine–pyrene conjugates as fluorescent probes for DNA/RNA and an inactive mutant of dipeptidyl peptidase enzyme

• Josipa Matić,
• Tana Tandarić,
• Marijana Radić Stojković,
• Filip Šupljika,
• Zrinka Karačić,
• Ana Tomašić Paić,
• Lucija Horvat,
• Robert Vianello and
• Lidija-Marija Tumir

Beilstein J. Org. Chem. 2023, 19, 550–565, doi:10.3762/bjoc.19.40

• were moderately soluble in DMSO (up to c = 1 × 10−3 mol dm−3) and their stock solutions were stable during a few months. All measurements were recorded in the Na cacodylate buffer (Ic = 0.05 mol dm−3) both at pH 5.0 and pH 7.0 for comparison, since the phenanthridine heterocyclic nitrogen becomes

• protonated in weakly acidic conditions (pH 5) [20][21]. The volume ratio of DMSO was less than 1% in all measurements. The absorbance of aqueous solutions for compounds Phen-Py-1 and Phen-Py-2 was proportional to their concentrations up to c = 1–2 × 10−5 mol dm−3. In contrast to the Lambert–Beer law, a

• : Solvents were distilled from appropriate drying agents shortly before use. TLC was carried out on DC-plastikfolien Kieselgel 60 F254 and preparative thick-layer (2 mm) chromatography was done on Merck 60 F254. 1H and 13C NMR spectra were recorded in DMSO-d6 or CDCl3 on Bruker AV 300 and 600 MHz

Transition-metal-catalyzed C–H bond activation as a sustainable strategy for the synthesis of fluorinated molecules: an overview

• Louis Monsigny,
• Floriane Doche and
• Tatiana Besset

Beilstein J. Org. Chem. 2023, 19, 448–473, doi:10.3762/bjoc.19.35

• acrylamide derivatives [140]. Using the same directing group, a panel of α-arylacrylamide derivatives 39a–f was successfully functionalized with a high Z-selectivity (yields up to 98%, Scheme 18). Both, thermal reaction conditions (DMSO at 70 °C for 16 h) and microwave irradiation (100 °C using microwaves in

Dipeptide analogues of fluorinated aminophosphonic acid sodium salts as moderate competitive inhibitors of cathepsin C

• Karolina Wątroba,
• Małgorzata Pawełczak and
• Marcin Kaźmierczak

Beilstein J. Org. Chem. 2023, 19, 434–439, doi:10.3762/bjoc.19.33

• result of the reactions carried out, the dipeptide analogues of α- and β-fluorinated aminophosphonic acids 8 and 10 were obtained. All the samples were solids, with very poor solubility in water and organic solvents such as DMSO and MeOH. The final step of the synthesis was the reaction of the resulting

CuAAC-inspired synthesis of 1,2,3-triazole-bridged porphyrin conjugates: an overview

• Dileep Kumar Singh

Beilstein J. Org. Chem. 2023, 19, 349–379, doi:10.3762/bjoc.19.29

• ascorbate in DMSO (Scheme 9). According to UV–vis and circular dichroism (CD) spectrum measurements, the authors state that the formation of the dimer of porphyrin 50 can be attributed to DNA hybridization and through-space electronic interactions. In this investigation, it was found that the DNA serves as

• porphyrin subunits and was more efficient in DMSO as compared to chloroform. Also, a clear evidence of a folded conformer was found by electrostatic and CH–π interactions, which was also, confirmed by density functional theory (DFT) calculations. In another report, meso-triazole-bridged porphyrin-carborane

• 124 in the presence of copper bromide and tris((1-benzyl-4-triazolyl)methyl)amine (TBTA) in DMSO/H2O to give a porphyrin-lantern (PL)-DNA sequence in 45% yield after cleavage and deprotection. These PL-DNA sequences were further used to construct strong and fluorescent G-wires that could be useful for

Synthesis and reactivity of azole-based iodazinium salts

• Thomas J. Kuczmera,
• Annalena Dietz,
• Andreas Boelke and
• Boris J. Nachtsheim

Beilstein J. Org. Chem. 2023, 19, 317–324, doi:10.3762/bjoc.19.27

• –O5: 2.898 Å, C8–I1–O1: 173.80°, C6–I1–O5: 167.75°, C6–I1–C8: 94.05°; for 5ax: I1–O3: 3.354 Å, I1–O5, 3.078 Å, C1–I1–O3: 154.71°, C8–I1–O5: 148.91°, C1–I1–C8: 94.53°. Derivatizations of the iodonium salt 5aa. a) Ac2O, CuSO4·5H2O, NaOAc, AcOH, 120 °C, 5 h; b) S8/Se/Te, Cs2CO3, DMSO, rt–100 °C, 2.5–24 h

Continuous flow synthesis of 6-monoamino-6-monodeoxy-β-cyclodextrin

• János Máté Orosz,
• Dóra Ujj,
• Petr Kasal,
• Gábor Benkovics and
• Erika Bálint

Beilstein J. Org. Chem. 2023, 19, 294–302, doi:10.3762/bjoc.19.25

• - [16], hydroxylamino- [17], or alkylamino-CDs [18], monosubstituted at position C-6. In addition, the tosyl functional group can be oxidized to an aldehyde using a non-nucleophilic base in dimethyl sulfoxide (DMSO) [19]. The monoaldehyde CDs can be further oxidized selectively to afford the

Strategies to access the [5-8] bicyclic core encountered in the sesquiterpene, diterpene and sesterterpene series

• Cécile Alleman,
• Charlène Gadais,
• Laurent Legentil and
• François-Hugues Porée

Beilstein J. Org. Chem. 2023, 19, 245–281, doi:10.3762/bjoc.19.23

• compound 123 was treated with CrCl2 in the presence of a catalytic amount of NiCl2 in DMSO and further oxidized under Swern conditions, aquatolide (4) was obtained in 43% yield over the two steps along with 50% recovery of the starting material 123. Of note, the initial strategy involved an intramolecular

An efficient metal-free and catalyst-free C–S/C–O bond-formation strategy: synthesis of pyrazole-conjugated thioamides and amides

• Shubham Sharma,
• Dharmender Singh,
• Sunit Kumar,
• Vaishali,
• Rahul Jamra,
• Naveen Banyal,
• Deepika,
• Chandi C. Malakar and
• Virender Singh

Beilstein J. Org. Chem. 2023, 19, 231–244, doi:10.3762/bjoc.19.22

• thioamidation reaction. After that, DMSO and NMP were also screened as solvents in the absence of base, but a longer reaction time was required for similar transformation (7 h) (entries 20 and 21, Table 1). A reaction of model substrates under neat conditions delivered product 1C in poor yield (entry 22, Table

• oxidative amidation reaction of pyrazole-3-carbaldehyde 1 and 2-aminopyridine (F) in the presence of TBHP in DMSO as a solvent at 130 °C (entry 1, Table 2). However, the reaction required longer time (20 h) for the completion, and afforded a product in 29% yield only. It was realized that the isolated

• reaction with 5.0 equiv of H2O2 in DMSO as the reaction medium under heating, whereas, a poor yield of the product was obtained (entry 8, Table 2). Moreover, different combinations of H2O2 and DMSO were examined for the oxidative amidation of pyrazole-3-carbaldehyde 1 (entries 9 and 10, Table 2

Investigation of cationic ring-opening polymerization of 2-oxazolines in the “green” solvent dihydrolevoglucosenone

• Solomiia Borova and
• Robert Luxenhofer

Beilstein J. Org. Chem. 2023, 19, 217–230, doi:10.3762/bjoc.19.21

• reasons [1]. Halogenated solvents such as chlorobenzene or dichloromethane are widely used in polymer production, but their toxicity and high energy consumption for synthesis make them unwanted for widespread commercial use. Many other dipolar solvents such as dimethyl sulfoxide (DMSO), N,N

Insight into oral amphiphilic cyclodextrin nanoparticles for colorectal cancer: comprehensive mathematical model of drug release kinetic studies and antitumoral efficacy in 3D spheroid colon tumors

• Sedat Ünal,
• Gamze Varan,
• Juan M. Benito,
• Yeşim Aktaş and
• Erem Bilensoy

Beilstein J. Org. Chem. 2023, 19, 139–157, doi:10.3762/bjoc.19.14

• cyclodextrin (CD) nanoparticles and CPT solution in DMSO were determined against CT26 mouse and HT29 human colon carcinoma cell lines at 48 h and 72 h. For this purpose, CT26 and HT29 cells were grown in cell flasks separately. Then, cells were seeded in a 96-well cell culture plate with an initial seeding

• incubated for 48 and 72 hours. Our previous research demonstrated that HT29 cells treated with 1.44 µM CPT after 48 hours of incubation had almost 50% viability [9]. Therefore, the lower and upper concentrations of CPT (0.4, 0.8, 1.6, 3.2, 6.4, and 12.8 µM) were examined in this study. Equal DMSO

• concentrations were applied to the cells as a separate group, and cell viability was normalized relative to the DMSO group. After 48 h and 72 h of incubation time, cell viability was determined by the WST-1 assay with a microplate reader at a wavelength of 450 nm. Cells that were incubated with the medium were

Synthesis and characterisation of new antimalarial fluorinated triazolopyrazine compounds

• Kah Yean Lum,
• Jonathan M. White,
• Daniel J. G. Johnson,
• Vicky M. Avery and
• Rohan A. Davis

Beilstein J. Org. Chem. 2023, 19, 107–114, doi:10.3762/bjoc.19.11

• -difluoroethanesulfinate (DFES) and zinc difluoromethanesulfinate (DFMS). In brief, a mixture of the respective scaffold, Diversinate™ (2 equiv), and TFA (5 equiv) in DMSO/CH2Cl2/H2O (5:5:2) was stirred for 30 min at room temperature and cooled to 4 °C. Then, aqueous tert-butyl hydroperoxide (TBHP, 70%, 3 equiv) was

• ™ derivatisations on triazolopyrazine scaffolds. In a manner analogous to [14], the scaffold (0.1 mmol) was dissolved in DMSO/CH2Cl2 (1:1, 250 µL:250 µL) before the addition of Diversinate™ (0.2 mmol, 2 equiv), TFA (40 μL, 0.5 mmol, 5 equiv) and filtered H2O (100 μL). The reaction mixture was stirred for 30 min at

NaI/PPh₃-catalyzed visible-light-mediated decarboxylative radical cascade cyclization of N-arylacrylamides for the efficient synthesis of quaternary oxindoles

• Dan Liu,
• Yue Zhao and
• Frederic W. Patureau

Beilstein J. Org. Chem. 2023, 19, 57–65, doi:10.3762/bjoc.19.5

• (Table 1, entry 11). These results indicate that the accessibility of the phosphorus center is important. Next, the solvent was investigated. Replacing acetonitrile with dimethyl sulfoxide (DMSO), or dimethylacetamide (DMA), or acetone, or ethyl acetate (EA), resulted in inferior yields (Table 1, entries

Improving the accuracy of ³¹P NMR chemical shift calculations by use of scaling methods

• William H. Hersh and
• Tsz-Yeung Chan

Beilstein J. Org. Chem. 2023, 19, 36–56, doi:10.3762/bjoc.19.4

• (O)CH3 27.4 [49]/28.61; (iPrO)2P(O)H 4.2 [43]/4.54; PMe3 −62 [44]/−61.58 [50]). We have also included chemical shifts in more polar solvents (i.e., DMSO and methanol) when those were the only reported values. The chemical shifts of two commonly used reference standards for 31P NMR calculations

• range of structural types than the trivalent compounds. A number of the compounds required inclusion of several conformational isomers, and for the cationic compounds, the counterions were included, and the experimental chemical shifts included compounds as pure liquids and as CDCl3, CH2Cl2, CH3CN, DMSO

Digyalipopeptide A, an antiparasitic cyclic peptide from the Ghanaian Bacillus sp. strain DE2B

• Adwoa P. Nartey,
• Aboagye K. Dofuor,
• Kofi B. A. Owusu,
• Anil S. Camas,
• Hai Deng,
• Marcel Jaspars and
• Kwaku Kyeremeh

Beilstein J. Org. Chem. 2022, 18, 1763–1771, doi:10.3762/bjoc.18.185

• acquired in DMSO-d6, together with the distortionless enhancement by polarization transfer (DEPT-135) and the 1H, 13C, multiplicity edited pulsed field gradient heteronuclear single quantum coherence (HSQC) spectra showed the presence of ten sp2-hybridized carbon resonances all of which were assigned to

• full details of all the NMR data with correlations can be found in Table S1 and Figures S22–S29 in Supporting Information File 1 but the summary for the data acquired in DMSO-d6 solvent is shown in Table 1. Subsequently, we dissolved compound 1 in deuterated chloroform, measured all 1D- and 2D NMR data

• and repeated the structure elucidation (see Supporting Information File 1, Table S2, and Figures S30–S37). The resultant structure confirmed the structural information initially obtained from the NMR data in DMSO-d6 solvent. High-resolution ESI mass spectrometry (HRESIMS) sequence tags Furthermore

Inclusion complexes of the steroid hormones 17β-estradiol and progesterone with β- and γ-cyclodextrin hosts: syntheses, X-ray structures, thermal analyses and API solubility enhancements

• Alexios I. Vicatos,
• Zakiena Hoossen and
• Mino R. Caira

Beilstein J. Org. Chem. 2022, 18, 1749–1762, doi:10.3762/bjoc.18.184

• 0.6 mm. 1H NMR spectroscopy Solution-state 1H NMR analyses were performed to quantify the stoichiometric ratios of the CD inclusion complexes, and all of the crystalline samples obtained by co-precipitation were dissolved in deuterated dimethyl sulfoxide (DMSO-d6) at 23 °C. These analyses were

Synthetic study toward tridachiapyrone B

• Morgan Cormier,
• Florian Hernvann and
• Michaël De Paolis

Beilstein J. Org. Chem. 2022, 18, 1741–1748, doi:10.3762/bjoc.18.183

• , treatment with KH in DMSO at room temperature caused the degradation of 17. Scarcely examined for this purpose, hydroxide of quaternary ammonium salt was next evaluated to promote the anionic oxy-Cope rearrangement with the prospect that non-coordinating organic cations could facilitate the transformation