Copper-catalyzed multicomponent reactions for the efficient synthesis of diverse spirotetrahydrocarbazoles

• Shao-Cong Zhan,
• Ren-Jie Fang,
• Jing Sun and
• Chao-Guo Yan

Beilstein J. Org. Chem. 2022, 18, 796–808, doi:10.3762/bjoc.18.80

• compound 3a (CCDC 2109578) and 4e (CCDC 2109579) were successfully determined by X-ray diffraction. It is pleased to find that the obtained spiro[carbazole-3,5'-pyrimidines] 4a–h have same cis-configuration to that of the above prepared spiro[carbazole-3,3'-indolines] 1a–j and spiro[carbazole-2,3

Synthesis of bis-spirocyclic derivatives of 3-azabicyclo[3.1.0]hexane via cyclopropene cycloadditions to the stable azomethine ylide derived from Ruhemann's purple

• Alexander S. Filatov,
• Olesya V. Khoroshilova,
• Anna G. Larina,
• Vitali M. Boitsov and
• Alexander V. Stepakov

Beilstein J. Org. Chem. 2022, 18, 769–780, doi:10.3762/bjoc.18.77

• made use of resources from the X-ray Diffraction Center, Computer Center, Center for Magnetic Resonance, Educational Resource Center of Chemistry, Center for Chemical Analysis and Materials of Saint-Petersburg State University. Funding We gratefully acknowledge the financial support from the Russian

An isoxazole strategy for the synthesis of 4-oxo-1,4-dihydropyridine-3-carboxylates

• Timur O. Zanakhov,
• Ekaterina E. Galenko,
• Mikhail S. Novikov and
• Alexander F. Khlebnikov

Beilstein J. Org. Chem. 2022, 18, 738–745, doi:10.3762/bjoc.18.74

• . According to the calculation results compounds 2 exist in the pyridone form in acetonitrile or chloroform solution (Table 1). All new compounds were characterized by 1H, 13C NMR and HRMS methods. Moreover, the structure of 2k was also confirmed by single-crystal X-ray diffraction analysis (Figure S1

• File 179: Experimental procedures, compound characterization data, X-ray diffraction experiment, and copies of NMR spectra of new compounds. Supporting Information File 180: Crystallographic information file for compound 2k. Funding We gratefully acknowledge the financial support of the Russian

• Science Foundation project 21-73-00019. This research was carried out using resources of the Centre for Magnetic Resonance, the Research Centre for X-ray Diffraction Studies, the Centre for Chemical Analysis and Materials, and the Computer Centre of the Science Park of Saint Petersburg State University.

Mechanochemical halogenation of unsymmetrically substituted azobenzenes

• Dajana Barišić,
• Mario Pajić,
• Ivan Halasz,
• Darko Babić and
• Manda Ćurić

Beilstein J. Org. Chem. 2022, 18, 680–687, doi:10.3762/bjoc.18.69

• from laboratory powder X-ray diffraction (PXRD) data (Figure 4 and Figures S31 and S32 in Supporting Information File 1), are similar to that of complex I1-I [51] in which the palladium center is bound to the MeCN and tosylate (OTs) via nitrogen and oxygen, respectively, and to the azobenzene via the

Tri(n-butyl)phosphine-promoted domino reaction for the efficient construction of spiro[cyclohexane-1,3'-indolines] and spiro[indoline-3,2'-furan-3',3''-indolines]

• Hui Zheng,
• Ying Han,
• Jing Sun and
• Chao-Guo Yan

Beilstein J. Org. Chem. 2022, 18, 669–679, doi:10.3762/bjoc.18.68

• major isomers 3l (Figure 1), 3s (Figure 2), and 3f’ (Figure 3) were determined by X-ray diffraction analysis. As can be seen from Figure 1 and Figure 2, the aryl group exists in the trans-position of the carbonyl group of the oxindole scaffold in the newly formed cyclohexyl ring. On the other hand, the

• compound 8a (Figure 5) was determined by X-ray diffraction analysis. From Figure 5, it can be seen that the two oxindole moieties exist on the trans-configuration. Therefore, this reaction showed very high diastereoselectivity. To explain the formation of the dispiro compounds 8, a plausible reaction

• are summarized in Table 3. Because there are three chiral carbon atoms in the molecule, several diastereoisomers can be formed in the reaction. The spiro[cyclohexane-1,3'-indolines] 5a–e were obtained in moderate to good yields. The single crystal structure of compound 5a was determined by X-ray

A study of the photochemical behavior of terarylenes containing allomaltol and pyrazole fragments

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

Beilstein J. Org. Chem. 2022, 18, 588–596, doi:10.3762/bjoc.18.61

• established by X-ray diffraction. Keywords: allomaltol; ESIPT process; photochemistry; pyrazoles; terarylenes; Introduction The investigation of the photochemical behavior of organic products is a significant part of modern materials science and technology. The UV-induced processes are extensively employed

• corresponding quinoxalines 15a–l in good yields (Scheme 5). The structure of 15a was confirmed by single-crystal X-ray diffraction (Figure 2) as a representative example. It should be noted that X-ray analysis of the final quinoxaline unambiguously proves the conversion of the allomaltol fragment into the

• good yields (Scheme 6). The structure of 15m was confirmed by single-crystal X-ray diffraction (Figure 3). It should be mentioned that other options for trapping of photogenerated unstable α-hydroxy-1,2-diketones are also possible. For example, reduction via NaBH3CN can be used as an alternative

Unusual highly diastereoselective Rh(II)-catalyzed dimerization of 3-diazo-2-arylidenesuccinimides provides access to a new dibenzazulene scaffold

• Anastasia Vepreva,
• Alexander S. Bunev,
• Andrey Yu. Kudinov,
• Grigory Kantin,
• Mikhail Krasavin and
• Dmitry Dar’in

Beilstein J. Org. Chem. 2022, 18, 533–538, doi:10.3762/bjoc.18.55

• Resonance, the Center for Chemical Analysis and Materials Research and the Center for X-ray Diffraction Methods of Saint Petersburg State University Research Park for obtaining the analytical data. Funding This research was supported by the Russian Science Foundation (project grant 20-13-00024).

Tosylhydrazine-promoted self-conjugate reduction–Michael/aldol reaction of 3-phenacylideneoxindoles towards dispirocyclopentanebisoxindole derivatives

• Sayan Pramanik and
• Chhanda Mukhopadhyay

Beilstein J. Org. Chem. 2022, 18, 469–478, doi:10.3762/bjoc.18.49

• each product, but the single crystal X-ray diffraction analysis confirmed the diastereoselectivity of 3. A single crystal of 3g was successfully obtained by slow evaporation of the solvent with the structure unequivocally confirmed by X-ray diffraction analysis (Figure 2). The single crystal X-ray

• diffraction analysis also revealed the presence of four chiral stereocenters with two oxindole moieties at 1,3-possition that are in trans orientation to the 2-benzoyl group and the 5-aryl group is in cis orientation (Figure 2). This observation proved that the most thermodynamically stable diastereomer was

Four bioactive new steroids from the soft coral Lobophytum pauciflorum collected in South China Sea

• Di Zhang,
• Zhe Wang,
• Xiao Han,
• Xiao-Lei Li,
• Zhong-Yu Lu,
• Bei-Bei Dou,
• Wen-Ze Zhang,
• Xu-Li Tang,
• Ping-Lin Li and
• Guo-Qiang Li

Beilstein J. Org. Chem. 2022, 18, 374–380, doi:10.3762/bjoc.18.42

• structurally related compounds reported in the literature. The absolute configuration of 1–3 was determined by X-ray diffraction. All the compounds have assessed the cytotoxicity against HL-60, K562, and Hela cells. Compound 1 showed weak cytotoxicity against K562 cells with an IC50 value of 19.03 μM. In

• addition, compound 1 also showed a moderate anti-inflammatory effect in zebrafish. Keywords: anti-inflammatory; cytotoxicity; Lobophytum pauciflorum; soft coral; steroids; X-ray diffraction; Introduction The unique and complicated marine environment makes soft corals a treasure-house of secondary

• NOESY correlations of H3-18 with H3-21 suggested the E geometry of Δ17(20). Finally, the absolute configuration of compound 1 was established by single-crystal X-ray diffraction analysis (Figure 4) carried out using Cu Kα radiation with a Flack parameter of 0.0(2). Compound 2, was isolated as a white

Unexpected chiral vicinal tetrasubstituted diamines via borylcopper-mediated homocoupling of isatin imines

• Marco Manenti,
• Leonardo Lo Presti,
• Giorgio Molteni and
• Alessandra Silvani

Beilstein J. Org. Chem. 2022, 18, 303–308, doi:10.3762/bjoc.18.34

• diastereoselectivity of the reaction (see Supporting Information File 1). All stereochemical implications were fully confirmed by single-crystal X-ray diffraction analysis, which was performed on well-formed prismatic crystals of compound 2a (Figure 1) [28]. Compound 2a is chiral and crystallizes in the orthorhombic

• determined by single-crystal X-ray diffraction analysis. Conclusion In summary, we have disclosed a reaction protocol that allows efficient homocoupling of oxindole-based N-tert-butanesulfinyl imines and generation of chiral, quaternary 1,2-diamines in a mild and completely stereoselective way. The one-pot

• products we disclosed the efficient homocoupling of oxindole-based N-tert-butanesulfinyl imines, with the generation of chiral, quaternary 1,2-diamines in a mild and completely stereoselective way. The obtained 3,3′-bisoxindole derivatives were fully characterized by NMR and single-crystal X-ray

Multi-faceted reactivity of N-fluorobenzenesulfonimide (NFSI) under mechanochemical conditions: fluorination, fluorodemethylation, sulfonylation, and amidation reactions

• José G. Hernández,
• Karen J. Ardila-Fierro,
• Dajana Barišić and
• Hervé Geneste

Beilstein J. Org. Chem. 2022, 18, 182–189, doi:10.3762/bjoc.18.20

• '' “remain[ed] obscure” [28]. In our case, we anticipated that formation of 2c'' could be accompanied by concomitant formation of (PhSO2)2NH and (PhSO2)2NCH3 derived from NFSI and 1c. For the analysis of the reaction mixture we selected powder X-ray diffraction (PXRD), a rapid analytical technique that has

• %; (SO2Ph)2NCH3 yield = 82%. (b) Powder X-ray diffraction (PXRD) patterns measured for the reactants and simulated PXRD patterns for the published (SO2Ph)2NCH3 (CCDC ZAJBIZ) and (SO2Ph)2NH (CCDC BSULFA). (c) 1H NMR analysis of the reaction mixture of the milling of 1c and NFSI (2.0 equiv) at 30 Hz for 3 h

Ready access to 7,8-dihydroindolo[2,3-d][1]benzazepine-6(5H)-one scaffold and analogues via early-stage Fischer ring-closure reaction

• Irina Kuznetcova,
• Felix Bacher,
• Daniel Vegh,
• Hsiang-Yu Chuang and
• Vladimir B. Arion

Beilstein J. Org. Chem. 2022, 18, 143–151, doi:10.3762/bjoc.18.15

• , characterization data and 1H and 13C NMR spectra of compounds, NMR numbering schemes and X-ray crystallography data. Acknowledgements We also thank Mr. Alexander Roller and Ms. Natalie Gajic for collection of X-ray diffraction data. Funding Support from the Austrian Science Fund (FWF) (P31293-N37) and Slovak

Green synthesis of C5–C6-unsubstituted 1,4-DHP scaffolds using an efficient Ni–chitosan nanocatalyst under ultrasonic conditions

• Soumyadip Basu,
• Sauvik Chatterjee,
• Suman Ray,
• Suvendu Maity,
• Prasanta Ghosh,
• Asim Bhaumik and
• Chhanda Mukhopadhyay

Beilstein J. Org. Chem. 2022, 18, 133–142, doi:10.3762/bjoc.18.14

• characterized by powder Fourier-transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD) analysis, scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), energy-dispersive X-ray (EDX) spectroscopy, etc. It was effectively utilized in the eco-friendly synthesis of

Regioselective synthesis of methyl 5-(N-Boc-cycloaminyl)-1,2-oxazole-4-carboxylates as new amino acid-like building blocks

• Jolita Bruzgulienė,
• Greta Račkauskienė,
• Aurimas Bieliauskas,
• Vaida Milišiūnaitė,
• Miglė Dagilienė,
• Gita Matulevičiūtė,
• Vytas Martynaitis,
• Sonata Krikštolaitytė,
• Frank A. Sløk and
• Algirdas Šačkus

Beilstein J. Org. Chem. 2022, 18, 102–109, doi:10.3762/bjoc.18.11

• analysis, 1H, 13C, and 15N NMR spectroscopy, HRMS, and single-crystal X-ray diffraction data. Keywords: β-enamino ketoesters; heterocyclic amino acids; 15N-labeled 1,2-oxazole; NMR (1H; 13C; 15N); 1,2-oxazole (isoxazole); X-ray structure analysis; Introduction 1,2-Oxazoles (isoxazoles) constitute an

• and 4g with trifluoroacetic acid. Removal of the Boc protection in the presence of CF3COOH in dichloromethane yielded trifluoroacetates 6a and 6b as white solids (Scheme 4). A single crystal of 6b was prepared via recrystallization from dichloromethane for X-ray diffraction analysis [48]. The

Efficient and regioselective synthesis of dihydroxy-substituted 2-aminocyclooctane-1-carboxylic acid and its bicyclic derivatives

• İlknur Polat,
• Selçuk Eşsiz,
• Uğur Bozkaya and
• Emine Salamci

Beilstein J. Org. Chem. 2022, 18, 77–85, doi:10.3762/bjoc.18.7

• -oxabicyclo[5.2.1]decan-10-yl)carbamate was confirmed by X-ray diffraction. Keywords: aminocyclitol; azidolysis; bicyclic β-lactam; bicyclic lactone; cyclic β-amino acids; DFT; Introduction Cyclic β-amino acids have for the past few decades aroused widespread synthetic interest owing to their diverse

Bifunctional thiourea-catalyzed asymmetric [3 + 2] annulation reactions of 2-isothiocyanato-1-indanones with barbiturate-based olefins

• Jiang-Song Zhai and
• Da-Ming Du

Beilstein J. Org. Chem. 2022, 18, 25–36, doi:10.3762/bjoc.18.3

• solubility of this substrate. The absolute configuration of the chiral product 3ae was unambiguously identified on the basis of single-crystal X-ray diffraction analysis as (2S,3'S) (Figure 4) [33]. The configurations of the other products were assigned by analogy to 3ae. In order to further prove the

Synthesis of a novel aminobenzene-containing hemicucurbituril and its fluorescence spectral properties with ions

• Qingkai Zeng,
• Qiumeng Long,
• Jihong Lu,
• Li Wang,
• Yuting You,
• Xiaoting Yuan,
• Qianjun Zhang,
• Qingmei Ge,
• Hang Cong and
• Mao Liu

Beilstein J. Org. Chem. 2021, 17, 2840–2847, doi:10.3762/bjoc.17.195

• X-ray diffraction analysis. As shown in Figure 1, the nitrobenzene-containing hemicucurbituril 9 adopted a square-cavity conformation. Notably, three nitrobenzene units shared nearly a plane. It should be highlighted that macrocycle 9 gave concise proton and carbon signals in the 1H and 13C NMR

Host–guest interaction and properties of cucurbit[8]uril with chloramphenicol

• Lin Zhang,
• Jun Zheng,
• Guangyan Luo,
• Xiaoyue Li,
• Yunqian Zhang,
• Zhu Tao and
• Qianjun Zhang

Beilstein J. Org. Chem. 2021, 17, 2832–2839, doi:10.3762/bjoc.17.194

• (CPE) was investigated using single-crystal X-ray diffraction spectroscopy, isothermal titration calorimetry (ITC) and UV–vis, NMR and IR spectroscopy. The effects of Q[8] on the stability, in vitro release performance and antibacterial activity of CPE were also studied. The results showed that CPE and

• ] and CPE was studied using single-crystal X-ray diffraction, UV–vis and 1H NMR spectroscopy, and the effects of Q[8] on the stability, in vitro release rate and antibacterial activity of CPE were investigated. Results and Discussion The host–guest interaction between Q[8] and CPE Single-crystal

• . Conclusion Herein, the 1:1 host–guest complex of CPE and Q[8] was confirmed using single-crystal X-ray diffraction and 1H NMR, UV–vis and IR spectroscopy. The CPE molecule completely enters the cavity of Q[8] with an inclusion constant of 5.474 × 105 L/mol. The intervention of Q[8] has no effect on the

Selective sulfonylation and isonitrilation of para-quinone methides employing TosMIC as a source of sulfonyl group or isonitrile group

• Chuanhua Qu,
• Run Huang,
• Yong Li,
• Tong Liu,
• Yuan Chen and
• Guiting Song

Beilstein J. Org. Chem. 2021, 17, 2822–2831, doi:10.3762/bjoc.17.193

• 3e was chosen as a representative compound and its structure was clearly verified by single crystal X-ray diffraction analysis, as shown in Figure 2 (CCDC No. 2104242). Next, the substrate scope of the 1,6-conjugate reaction of TosMIC to p-QMs was examined under optimized conditions (Table 1, entry

Biological properties and conformational studies of amphiphilic Pd(II) and Ni(II) complexes bearing functionalized aroylaminocarbo-N-thioylpyrrolinate units

• Samet Poyraz,
• Samet Belveren,
• Sabriye Aydınoğlu,
• Mahmut Ulger,
• Abel de Cózar,
• Maria de Gracia Retamosa,
• Jose M. Sansano and
• H. Ali Döndaş

Beilstein J. Org. Chem. 2021, 17, 2812–2821, doi:10.3762/bjoc.17.192

• the cis-configuration determined according to X-ray diffraction patterns observed in precedent works [15][16]. Although a structural motif of the metallosurfactants is having a long alkyl chain (hydrophobic part), in these cases, L1–L3 possessed four hydrophobic domains, which are responsible of the

• causing of the selective formation of the cis- versus the trans-aggregate observed after X-ray diffraction analysis, but calculations did not give any clear interaction to confirm it. The polar solvent methanol used for the reaction and separation could favor this chemical arrangement. Ligands L1 and L3

Photophysical, photostability, and ROS generation properties of new trifluoromethylated quinoline-phenol Schiff bases

• Inaiá O. Rocha,
• Yuri G. Kappenberg,
• Wilian C. Rosa,
• Clarissa P. Frizzo,
• Nilo Zanatta,
• Marcos A. P. Martins,
• Isadora Tisoco,
• Bernardo A. Iglesias and
• Helio G. Bonacorso

Beilstein J. Org. Chem. 2021, 17, 2799–2811, doi:10.3762/bjoc.17.191

• solution and no signal belonging to the Z isomer was observed in all cases, which can be confirmed by the chemical shift values in the 1H NMR regarding the –CH=N bond. Finally, in order to determine the real molecular structure of the Schiff bases 3, single-crystal X-ray diffraction (SC-XRD) was performed

The PIFA-initiated oxidative cyclization of 2-(3-butenyl)quinazolin-4(3H)-ones – an efficient approach to 1-(hydroxymethyl)-2,3-dihydropyrrolo[1,2-a]quinazolin-5(1H)-ones

• Alla I. Vaskevych,
• Nataliia O. Savinchuk,
• Ruslan I. Vaskevych,
• Eduard B. Rusanov,
• Oleksandr O. Grygorenko and
• Mykhailo V. Vovk

Beilstein J. Org. Chem. 2021, 17, 2787–2794, doi:10.3762/bjoc.17.189

• product 6. The structure of products 6 was confirmed by NMR spectroscopy; in addition to that, X-ray diffraction studies were performed with single crystals of compound 6f (see Figure 2). Since the application of the obtained compounds in early drug discovery is anticipated, it is important to assess

Solvent-free synthesis of enantioenriched β-silyl nitroalkanes under organocatalytic conditions

• Akhil K. Dubey and
• Raghunath Chowdhury

Beilstein J. Org. Chem. 2021, 17, 2642–2649, doi:10.3762/bjoc.17.177

• was found to adopt “(S)” configuration which was unambiguously established by single crystal X-ray diffraction analysis (Figure 1) [45]. To prove the scalability of this synthetic method, we examined the synthesis of 3c and ent-3d in a 1 mmol scale (Scheme 5). The products 3c and ent-3d were isolated

Synthesis of new bile acid-fused tetrazoles using the Schmidt reaction

• Dušan Đ. Škorić,
• Olivera R. Klisurić,
• Dimitar S. Jakimov,
• Marija N. Sakač and
• János J. Csanádi

Beilstein J. Org. Chem. 2021, 17, 2611–2620, doi:10.3762/bjoc.17.174

• different ketone and enone precursors from cholic acid, deoxycholic acid, and chenodeoxycholic acid was established. Newly obtained tetrazole derivatives were characterized by NMR and X-ray diffraction spectroscopy. In a number of cases, preliminary antiproliferative tests of new compounds showed strong and

Efficient synthesis of polyfunctionalized carbazoles and pyrrolo[3,4-c]carbazoles via domino Diels–Alder reaction

• Ren-Jie Fang,
• Chen Yan,
• Jing Sun,
• Ying Han and
• Chao-Guo Yan

Beilstein J. Org. Chem. 2021, 17, 2425–2432, doi:10.3762/bjoc.17.159

• crystal structure of compound 4g was determined by X-ray diffraction (Figure 4). It can be seen that the ring of pyrrolo[3,4-c]carbazole exists in a slightly twisted plane. The dihedral angles of the phenyl and the benzoyl group to the central benzene ring are 72.018° and 88.402°. To further expand the