Confirmation of the stereochemistry of spiroviolene

• Yao Kong,
• Yuanning Liu,
• Kaibiao Wang,
• Tao Wang,
• Chen Wang,
• Ben Ai,
• Hongli Jia,
• Guohui Pan,
• Min Yin and
• Zhengren Xu

Beilstein J. Org. Chem. 2024, 20, 852–858, doi:10.3762/bjoc.20.77

• , direct evidences such as single-crystal X-ray diffraction results were not reported in their study. The reassignment of the stereochemistry at C3 has resulted in the revision of the proposed cyclization mechanism [12][13][14]. The revised mechanism resembled the cyclization process for the formation of

• the fermentation broth. The physicochemical data of the isolated material are consistent with those reported for spiroviolene [6]. With sufficient amount of spiroviolene in hand, we next attempted to obtain a crystalline compound suitable for X-ray diffraction by introducing functional groups (e.g., a

• suitable for X-ray diffraction [35]. The crystal structure of 13 clearly showed that the 19- and 20-methyl groups are cis-oriented in the D-ring which is consistent with that of spirograterpene A. This structural data reaffirms the revised structure of spiroviolene, and further support the unified

Production of non-natural 5-methylorsellinate-derived meroterpenoids in Aspergillus oryzae

• Jia Tang,
• Yixiang Zhang and
• Yudai Matsuda

Beilstein J. Org. Chem. 2024, 20, 638–644, doi:10.3762/bjoc.20.56

• the complete structural determination of 3. To overcome this challenge in structural determination, we obtained a single crystal of 3 and performed X-ray diffraction analysis, which unambiguously established the structure of 3 as 5′-desmethylpreterretonin A (Figure 2C and Figure S1 in Supporting

• . Finally, the A. oryzae strain expressing insA7 produced two major metabolites 7 and 8. Compound 7 was determined to be the C-5′ desmethyl form of insuetusin A1 [19] using NMR and single-crystal X-ray diffraction analyses (Figure 2C and Figure S1 in Supporting Information File 1; CCDC: 2300695) and was

• . Man-Kit Tse (City University of Hong Kong) and Dr. Shek-Man Yiu (City University of Hong Kong) for their assistance in NMR spectra acquisition and X-ray diffraction data collection and analysis, respectively. Funding This work was supported by a General Research Fund grant from the Research Grants

A laterally-fused N-heterocyclic carbene framework from polysubstituted aminoimidazo[5,1-b]oxazol-6-ium salts

• Andrew D. Gillie,
• Matthew G. Wakeling,
• Bethan L. Greene,
• Louise Male and
• Paul W. Davies

Beilstein J. Org. Chem. 2024, 20, 621–627, doi:10.3762/bjoc.20.54

• the C(oxazole)–N(sulfonamide) bond. No coalescence is observed at up to 110 °C indicating that these motifs might be useful as a robust atropisomeric system. The molecular structure of 13 and 14 have been unambiguously determined by single crystal X-ray diffraction (Scheme 2) [28]. The N–metal

• complexes from 6a. The single crystal X-ray diffraction structures of 13 and 14 have ellipsoids drawn at 50% probability, with hydrogens and solvent omitted for clarity. Selected bond angles and distances: 13: C1–Au: 1.98 Å, Au–Cl: 2.28 Å, N2–Au: 3.65 Å. N1–C1–N3: 102.7°, N3–C1–Au: 129.5°, N1–C1–Au: 127.1

Entry to new spiroheterocycles via tandem Rh(II)-catalyzed O–H insertion/base-promoted cyclization involving diazoarylidene succinimides

• Alexander Yanovich,
• Anastasia Vepreva,
• Ksenia Malkova,
• Grigory Kantin and
• Dmitry Dar’in

Beilstein J. Org. Chem. 2024, 20, 561–569, doi:10.3762/bjoc.20.48

• procedures, analytical data and NMR spectra for the reported compounds. Acknowledgements We thank the Research Center for Magnetic 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

Synthesis of photo- and ionochromic N-acylated 2-(aminomethylene)benzo[b]thiophene-3(2Н)-ones with a terminal phenanthroline group

• Vladimir P. Rybalkin,
• Sofiya Yu. Zmeeva,
• Lidiya L. Popova,
• Irina V. Dubonosova,
• Olga Yu. Karlutova,
• Oleg P. Demidov,
• Alexander D. Dubonosov and
• Vladimir A. Bren

Beilstein J. Org. Chem. 2024, 20, 552–560, doi:10.3762/bjoc.20.47

• products 3a–c were comprehensively characterized by IR, 1Н and 13C NMR spectroscopy, HRMS (Supporting Information File 2) as well as by X-ray diffraction analysis. The molecular structure of 3b is shown in Figure 3. The crystal data, details of the data collection and refinements for 3b as well as complete

• , HRMS and X-ray diffraction analysis. Selectively, Fe2+ caused an appearance of new broad long-wavelength absorption bands at 480−530 nm with a contrast naked-eye effect: a visually distinguishable color change of the solutions from yellow to dark orange. The obtained complexes with Fe2+ in acetonitrile

• ™ Impact instrument (electrospray ionization). Melting points were determined on a Fisher–Johns melting point apparatus. X-ray diffraction study The X-ray diffraction dataset of compound 3b was recorded on an Agilent SuperNova diffractometer using a microfocus X-ray radiation source with copper anode and

Pseudallenes A and B, new sulfur-containing ovalicin sesquiterpenoid derivatives with antimicrobial activity from the deep-sea cold seep sediment-derived fungus Pseudallescheria boydii CS-793

• Zhen Ying,
• Xiao-Ming Li,
• Sui-Qun Yang,
• Hong-Lei Li,
• Xin Li,
• Bin-Gui Wang and
• Ling-Hong Meng

Beilstein J. Org. Chem. 2024, 20, 470–478, doi:10.3762/bjoc.20.42

• compound 1, crystals suitable for X-ray crystal analysis were obtained by slow evaporation of the solvent, which could be analyzed by X-ray diffraction analysis using Cu Kα radiation (Figure 4). The resulting Flack parameter, 0.019(6), allowed the assignment of the absolute configurations of all the

• verified by the COSY and HMBC correlations (Figure 2). The structure and relative configuration of compound 2 were deduced the same as for 1 by NOE correlations (Figure 3). Moreover, the absolute configurations of compound 2 were unambiguous determined by X-ray diffraction with the refined Flack parameter

• data for compound 3 was conducted (Table 1) and its absolute configurations were assigned as 1R, 2S, 6R, 7R, 8S by single-crystal X-ray diffraction analysis with a Flack parameter of 0.024(6) (Figure 4). A plausible biosynthetic pathway for compounds 1–5 is proposed as shown in Scheme 1. In this

Facile approach to N,O,S-heteropentacycles via condensation of sterically crowded 3H-phenoxazin-3-one with ortho-substituted anilines

• Eugeny Ivakhnenko,
• Vasily Malay,
• Pavel Knyazev,
• Nikita Merezhko,
• Nadezhda Makarova,
• Oleg Demidov,
• Gennady Borodkin,
• Andrey Starikov and
• Vladimir Minkin

Beilstein J. Org. Chem. 2024, 20, 336–345, doi:10.3762/bjoc.20.34

• were rendered and prepared for publication with the Olex2 version 1.3.0 software suite [31]. The complete X-ray diffraction datasets were deposited in the Cambridge Crystallographic Data Center (CCDC numbers 2292841, 2292840, 2292847, 2308520, and 2292848, Tables S2–S9, Supporting Information File 1

Photochromic derivatives of indigo: historical overview of development, challenges and applications

• Gökhan Kaplan,
• Zeynel Seferoğlu and
• Daria V. Berdnikova

Beilstein J. Org. Chem. 2024, 20, 228–242, doi:10.3762/bjoc.20.23

• melting point of indigo is bifurcated intra- and intermolecular hydrogen bonding [11], and face-to-face π–π stacking of parallel aromatic rings (Figure 2) [12]. Single crystal X-ray diffraction analysis showed that the indigo molecule is almost planar and exists in the E-conformation. The central C=C bond

• used in the synthesis of indigo [4]. a) Intramolecular (a = 2.26 Å) and intermolecular (b = 2.11 Å) hydrogen bonds in indigo, b) crystal packing of indigo in the solid state obtained from the single-crystal X-ray diffraction data, CCDC 796873 [12], c) photos of indigo in the solid state and solutions

Comparison of glycosyl donors: a supramer approach

• Anna V. Orlova,
• Nelly N. Malysheva,
• Maria V. Panova,
• Nikita M. Podvalnyy,
• Michael G. Medvedev and
• Leonid O. Kononov

Beilstein J. Org. Chem. 2024, 20, 181–192, doi:10.3762/bjoc.20.18

• treated with 90% aq trifluoroacetic acid in CH2Cl2 to give diol 7 (70% yield) that was formed due to migration of a chloroacetyl group from O-7 to O-9. The structure of diol 7 was established by NMR spectroscopy, high-resolution mass spectrometry and X-ray diffraction analysis (see the Experimental

Perspectives on push–pull chromophores derived from click-type [2 + 2] cycloaddition–retroelectrocyclization reactions of electron-rich alkynes and electron-deficient alkenes

• Michio Yamada

Beilstein J. Org. Chem. 2024, 20, 125–154, doi:10.3762/bjoc.20.13

Multi-redox indenofluorene chromophores incorporating dithiafulvene donor and ene/enediyne acceptor units

• Christina Schøttler,
• Kasper Lund-Rasmussen,
• Line Broløs,
• Philip Vinterberg,
• Ema Bazikova,
• Viktor B. R. Pedersen and
• Mogens Brøndsted Nielsen

Beilstein J. Org. Chem. 2024, 20, 59–73, doi:10.3762/bjoc.20.8

• Crystals suitable for single-crystal X-ray diffraction studies were obtained for compounds 25, 26, and 29. Their structures are shown in Figure 10, top, and their respective crystal packings below. All three compounds pack in a herringbone manner in the crystal structure, with the major difference that

• after the experiment. A 0.1 M solution of NBu4PF6 was used as electrolyte. All solutions were purged with Ar prior to measurements. Crystallography All single crystal X-ray diffraction data for compounds 25, 26, and 29 were collected on a Bruker D8 VENTURE diffractometer equipped with a Mo Kα X-ray (λ

Using the phospha-Michael reaction for making phosphonium phenolate zwitterions

• Matthias R. Steiner,
• Max Schmallegger,
• Larissa Donner,
• Johann A. Hlina,
• Christoph Marschner,
• Judith Baumgartner and
• Christian Slugovc

Beilstein J. Org. Chem. 2024, 20, 41–51, doi:10.3762/bjoc.20.6

• in these cases (Supporting Information File 1, Figures S54 and S74). Crystal structures The solid-state structures of 2a and 2f were determined by single-crystal X-ray diffraction. The crystals were grown from concentrated solutions in toluene. A representation of the molecular structure of 2a is

Aldiminium and 1,2,3-triazolium dithiocarboxylate zwitterions derived from cyclic (alkyl)(amino) and mesoionic carbenes

• Nedra Touj,
• François Mazars,
• Guillermo Zaragoza and
• Lionel Delaude

Beilstein J. Org. Chem. 2023, 19, 1947–1956, doi:10.3762/bjoc.19.145

• cyclic (alkyl)(amino) or mesoionic carbenes (CAACs or MICs) onto carbon disulfide. Nine novel compounds were isolated and fully characterized by 1H and 13C NMR, FTIR, and HRMS techniques. Moreover, the molecular structures of two CAAC·CS2 and two MIC·CS2 betaines were determined by X-ray diffraction

• . Crystallography Crystals of CAAC·CS2 zwitterions 4a and 4c suitable for X-ray diffraction (XRD) analysis were grown by slow diffusion of cyclohexane in a THF solution at 6 °C. Their molecular structures are depicted in Figure 3. The orange-red needles of compound 4a belonged to the trigonal space group, while

• betaines were determined by X-ray diffraction analysis. The various analytical data recorded for all these compounds were compared with those reported previously for related NHC·CS2 zwitterions derived from imidazolinium or (benz)imidazolium salts. Due to the absence of electronic communication between the

Construction of diazepine-containing spiroindolines via annulation reaction of α-halogenated N-acylhydrazones and isatin-derived MBH carbonates

• Xing Liu,
• Wenjing Shi,
• Jing Sun and
• Chao-Guo Yan

Beilstein J. Org. Chem. 2023, 19, 1923–1932, doi:10.3762/bjoc.19.143

• yields. The chemical structures of the spiro compounds 7a–n were established by various spectroscopy methods. In addition, the single crystal structure of compound 7a was also determined by X-ray diffraction (Figure 1). As can be seen from Figure 1, both the C–C and C–N double bonds are part of the

Controlling the reactivity of La@C₈₂ by reduction: reaction of the La@C₈₂ anion with alkyl halide with high regioselectivity

• Yutaka Maeda,
• Saeka Akita,
• Mitsuaki Suzuki,
• Michio Yamada,
• Takeshi Akasaka,
• Kaoru Kobayashi and
• Shigeru Nagase

Beilstein J. Org. Chem. 2023, 19, 1858–1866, doi:10.3762/bjoc.19.138

• and visible–near infrared spectroscopy. The reaction of La@C2v-C82 with alkyl halides using the same conditions showed no consumption of La@C2v-C82, indicating that the reactivity of La@C2v-C82 toward alkyl halides was effectively increased by one-electron reduction. Single-crystal X-ray diffraction

• @C2v-C82(CHClC6H3Cl2) [19] and La@C2v-C82(CBr(CO2Et)2) [23], by single-crystal X-ray diffraction (SC-XRD) analysis. Based on the similarity in the absorption spectra of La@C2v-C82(CHClC6H3Cl2), the addition site of 3a–c was expected to be at the C10 (for the numbering of carbon atoms in La@C2v-C82; see

N-Boc-α-diazo glutarimide as efficient reagent for assembling N-heterocycle-glutarimide diads via Rh(II)-catalyzed N–H insertion reaction

• Grigory Kantin,
• Pavel Golubev,
• Alexander Sapegin,
• Alexander Bunev and
• Dmitry Dar’in

Beilstein J. Org. Chem. 2023, 19, 1841–1848, doi:10.3762/bjoc.19.136

• : General experimental information, X-ray crystallographic data, synthetic procedures, analytical data and NMR spectra for the reported compounds. Acknowledgements We thank the Research Center for Magnetic 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 22-13-00005).

Charge carrier transport in perylene-based and pyrene-based columnar liquid crystals

• Alessandro L. Alves,
• Simone V. Bernardino,
• Carlos H. Stadtlober,
• Edivandro Girotto,
• Giliandro Farias,
• Rodney M. do Nascimento,
• Sergio F. Curcio,
• Thiago Cazati,
• Marta E. R. Dotto,
• Juliana Eccher,
• Leonardo N. Furini,
• Hugo Gallardo,
• Harald Bock and
• Ivan H. Bechtold

Beilstein J. Org. Chem. 2023, 19, 1755–1765, doi:10.3762/bjoc.19.128

• 1758 cm−1 (C=O). X-ray diffraction (XRD) measurements of 1 and 2 are shown in Figure 2. The Miller indices indicate the Colhex and Colrect character of the mesophases [31]. Despite crystallization of 2, the Colrect order is partially preserved at room temperature. The Colhex lattice parameter (a

Effects of the aldehyde-derived ring substituent on the properties of two new bioinspired trimethoxybenzoylhydrazones: methyl vs nitro groups

• Dayanne Martins,
• Roberta Lamosa,
• Talis Uelisson da Silva,
• Carolina B. P. Ligiero,
• Sérgio de Paula Machado,
• Daphne S. Cukierman and
• Nicolás A. Rey

Beilstein J. Org. Chem. 2023, 19, 1713–1727, doi:10.3762/bjoc.19.125

• were used to calculate the percentage decrease in concentration of the compound with respect to the first reading and data were processed using the OriginPro 21 software. X-ray diffraction Single crystals of hdz-CH3 and hdz-NO2 suitable for X-ray diffraction were obtained from the slow evaporation of

• the Federal Fluminense University (LDRX-UFF: http://ldrx.sites.uff.br/) for the X-ray diffraction facilities. Funding SPM, DSC and NAR thank the scientific Brazilian funding agency CNPq (Conselho Nacional de Desenvolvimento Científico e Tecnológico) - 304105/2021-0, 150898/2022-3 and 306866/2021-8

Benzoimidazolium-derived dimeric and hydride n-dopants for organic electron-transport materials: impact of substitution on structures, electrochemistry, and reactivity

• Swagat K. Mohapatra,
• Khaled Al Kurdi,
• Samik Jhulki,
• Georgii Bogdanov,
• John Bacsa,
• Maxwell Conte,
• Tatiana V. Timofeeva,
• Seth R. Marder and
• Stephen Barlow

Beilstein J. Org. Chem. 2023, 19, 1651–1663, doi:10.3762/bjoc.19.121

• derivatives (including 1bH, the structure of which has previously been reported, but with somewhat lower precision than in the present work [34]), and three salts of 1+ cations using single-crystal X-ray diffraction. Here, we briefly discuss some of the more interesting structural findings; a more detailed

Cyclization of 1-aryl-4,4,4-trichlorobut-2-en-1-ones into 3-trichloromethylindan-1-ones in triflic acid

• Vladislav A. Sokolov,
• Andrei A. Golushko,
• Irina A. Boyarskaya and
• Aleksander V. Vasilyev

Beilstein J. Org. Chem. 2023, 19, 1460–1470, doi:10.3762/bjoc.19.105

• spectra. Acknowledgements Spectral studies were performed at the Center for Magnetic Resonance, Center for Chemical Analysis and Materials Research, and the Research Center for X-ray Diffraction Studies of Saint Petersburg State University, Saint Petersburg, Russia. Funding This work was supported by the

Visible-light-induced nickel-catalyzed α-hydroxytrifluoroethylation of alkyl carboxylic acids: Access to trifluoromethyl alkyl acyloins

• Feng Chen,
• Xiu-Hua Xu,
• Zeng-Hao Chen,
• Yue Chen and
• Feng-Ling Qing

Beilstein J. Org. Chem. 2023, 19, 1372–1378, doi:10.3762/bjoc.19.98

• sterically hindered tertiary carboxylic acids were unfortunately not compatible with the reaction conditions. The structures of products 3a and 3s were unambiguously confirmed by single-crystal X-ray diffraction. Notably, the reaction of 1a could be easily scaled up to 1.0 mmol scale, affording 3a in a

Organic thermally activated delayed fluorescence material with strained benzoguanidine donor

• Alexander C. Brannan,
• Elvie F. P. Beaumont,
• Nguyen Le Phuoc,
• George F. S. Whitehead,
• Mikko Linnolahti and
• Alexander S. Romanov

Beilstein J. Org. Chem. 2023, 19, 1289–1298, doi:10.3762/bjoc.19.95

• isomeric mixture of 4BGIPN. This is expectedly higher than the analogous Tg of 176 °C for the 4CzIPN material [13] due to a lower molecular mass of the latter (Figure S1, Supporting Information File 1). Single crystals for X-ray diffraction study were obtained by slow layer diffusion of hexanes into

• the pure product as a yellow powder in 70% yield (450 mg, 474 μmol). Single crystals suitable for X-ray diffraction were grown by layering a concentrated solution in DCM with hexane which was left for slow evaporation. 1H NMR (700 MHz, DMSO-d6) δ 8.46–8.35 (m), 8.23–8.22 (m), 8.16–8.06 (m), 7.94–6.86

• ppm; Anal. calcd. for C60H32N14 (948.29): C, 75.94; H, 3.40; N, 20.66; found: C, 75.59; H, 3.54; N, 20.28; HRESIMS m/z: [M + Na]+ calcd. for C60H32N14Na, 971.2827; found, 971.2854. X-ray crystallography Crystals suitable for X-ray diffraction study were obtained by slow layer diffusion of hexanes

Selective construction of dispiro[indoline-3,2'-quinoline-3',3''-indoline] and dispiro[indoline-3,2'-pyrrole-3',3''-indoline] via three-component reaction

• Ziying Xiao,
• Fengshun Xu,
• Jing Sun and
• Chao-Guo Yan

Beilstein J. Org. Chem. 2023, 19, 1234–1242, doi:10.3762/bjoc.19.91

• different reactivity to that of the adducts of 3-ethoxycarbonylmethyleneoxindoles. For confirming the chemical structures of dispirooxindoles 4a–i, the single crystal structure of compound 4a was determined by X-ray diffraction (Figure 2). In Figure 2, the two oxindole scaffolds are in trans-position. The

Cyanothioacetamides as a synthetic platform for the synthesis of aminopyrazole derivatives

• Valeriy O. Filimonov,
• Alexandra I. Topchiy,
• Vladimir G. Ilkin,
• Tetyana V. Beryozkina and
• Vasiliy A. Bakulev

Beilstein J. Org. Chem. 2023, 19, 1191–1197, doi:10.3762/bjoc.19.87

• pyrazoles has been thus synthesized. The structure of the reaction products was studied using NMR spectroscopy and mass spectrometry and confirmed by X-ray diffraction analysis. Keywords: aminopyrazoles; 2-cyanothioacetamides; enamines; hydrazines; Introduction Compounds containing a pyrazole cycle

• group during the reaction. The structures of compounds 5a–e were confirmed by 1H and 13C NMR spectroscopy and HRMS, as well as X-ray diffraction analysis of a single crystal of compound 5b. The involvement of arylhydrazines 3b,c in the reaction with enamines 2a–d similarly leads to the formation of 1

• upon addition of hydrochloric acid. This is probably due to the protonation of the dimethylamino moiety or/and that dimethylamine hydrochloride is a better leaving group than the free base. The structures of compounds 6a–f were confirmed by 1H and 13C NMR spectroscopy and HRMS, as well as X-ray

CO₂ complexation with cyclodextrins

• Cecilie Høgfeldt Jessen,
• Jesper Bendix,
• Theis Brock Nannestad,
• Heloisa Bordallo,
• Martin Jæger Pedersen,
• Christian Marcus Pedersen and
• Mikael Bols

Beilstein J. Org. Chem. 2023, 19, 1021–1027, doi:10.3762/bjoc.19.78

• carried out on single crystals, which were coated with mineral oil, mounted on kapton loops, and transferred to the nitrogen cold stream of the diffractometer. The single-crystal X-ray diffraction studies were performed at 100(2) K on a Bruker D8 VENTURE diffractometer equipped with a Mo Kα high