Synthesis of indano[60]fullerene thioketone and its application in organic solar cells

• Yong-Chang Zhai,
• Shimon Oiwa,
• Shinobu Aoyagi,
• Shohei Ohno,
• Tsubasa Mikie,
• Jun-Zhuo Wang,
• Hirofumi Amada,
• Koki Yamanaka,
• Kazuhira Miwa,
• Naoyuki Imai,
• Takeshi Igarashi,
• Itaru Osaka and
• Yutaka Matsuo

Beilstein J. Org. Chem. 2024, 20, 1270–1277, doi:10.3762/bjoc.20.109

• -withdrawing substituents. Computational studies with density functional theory revealed the unique vibrations of the thioketone group in FIDS. The molecular structure of FIDS was confirmed by single-crystal X-ray analysis. Bulk heterojunction organic solar cells using three evaporable fullerene derivatives

Synthesis and optical properties of bis- and tris-alkynyl-2-trifluoromethylquinolines

• Stefan Jopp,
• Franziska Spruner von Mertz,
• Peter Ehlers,
• Alexander Villinger and
• Peter Langer

Beilstein J. Org. Chem. 2024, 20, 1246–1255, doi:10.3762/bjoc.20.107

• group, could not be isolated at all, since the reaction resulted in an inseparable mixture of several products. The structure of 6b could be independently confirmed by X-ray crystallography (Figure 2). Both phenyl rings are found to be twisted in an angle of approximately 45° from the quinoline core. As

• the 6-position in comparison to the 8-position. The structure of product 9f was confirmed by X-ray crystallography (Figure 3). The thiophene ring in 4-position is in plane with the quinoline core, while the other ring is twisted in an angle of approximately 85°. This might be explained by an

• dehalogenation at position 3. In particular, the side-product 6b was isolated in 25% yield during the purification of 12b. The structure of product 12d was proven by X-ray crystallography (Figure 4). All three phenyl rings are found to be nearly in plane with the quinoline core, showing only a slight twist of 5

Competing electrophilic substitution and oxidative polymerization of arylamines with selenium dioxide

• Vishnu Selladurai and
• Selvakumar Karuthapandi

Beilstein J. Org. Chem. 2024, 20, 1221–1235, doi:10.3762/bjoc.20.105

• , and methyl anthranilate, with selenium dioxide in acetonitrile. A systematic analysis of the reaction products with the help of 77Se NMR and single-crystal X-ray crystallography revealed that the reaction progress follows three major reaction pathways, electrophilic selenation, oxidative

• electrons over the adjacent carboxylate function, which prompted the selenation pathway, leading to the formation of two of the isomeric diorganyl selenides of methyl anthranilate. The diaryl selenides were structurally characterized using single-crystal X-ray diffraction. Density functional theory

• with arylamines follows a complex reaction pathway, leading to a mixture of compounds. We established the possible reaction pathways using 77Se NMR spectroscopy and single-crystal X-ray crystallographic studies. Density functional theory (DFT) calculations were carried out to understand the relative

Introduction of peripheral nitrogen atoms to cyclo-meta-phenylenes

• Koki Ikemoto and
• Hiroyuki Isobe

Beilstein J. Org. Chem. 2024, 20, 1207–1212, doi:10.3762/bjoc.20.103

• achieved with one-pot Suzuki–Miyaura coupling to arrange phenylene rings and pyridinylene rings in an alternating fashion. Analyses with UV–vis spectroscopy showed changes in the photophysical properties with nitrogen doping, and X-ray crystallographic analyses experimentally revealed the presence of

• biased charges on the peripheral nitrogen atoms. Keywords: cross coupling; macrocycles; nitrogen doping; UV–vis spectroscopy; X-ray charge density analysis; Introduction Graphitic carbonaceous sheets of graphene continue to attract considerable attention, which lead us to explore structural defects

• nitrogen-doped [n]CMPs (3) containing outward-radiating nitrogen dopants. The properties and structures were investigated with UV–vis spectroscopy and X-ray crystallography, which revealed the fundamental properties of the nitrogen dopants in the macrocyclic structures. Results and Discussion Nitrogen

Two-fold addition reaction of silylene to C₆₀: structural and electronic properties of a bis-adduct

• Masahiro Kako,
• Masato Kai,
• Masanori Yasui,
• Michio Yamada,
• Yutaka Maeda and
• Takeshi Akasaka

Beilstein J. Org. Chem. 2024, 20, 1179–1188, doi:10.3762/bjoc.20.100

• 305-8577, Japan 10.3762/bjoc.20.100 Abstract The addition reaction of C60 with silylene 1, a silicon analog of carbene, yielded the corresponding bis-adduct 3. The structure of 3 was determined by single-crystal X-ray structure analysis, representing the first example of a crystal structure of a

• -silylene adduct 3 of C60 based on spectroscopic measurements, X-ray crystallography, electrochemical analyses, and theoretical calculations. Results and Discussion Synthesis of bis-silylene adduct 3 The synthesis of the silylene adduct was conducted using a modified literature procedure [15]. A degassed

• ions of 3. Finally, the structure of 3 was established by single-crystal X-ray structure analysis. The ORTEP diagram of 3 is presented in Figure 5 with the selected bond lengths and angles collected in Table 1. The cage C–C bond lengths of the addition sites are C1–C9: 1.623(2) Å and C21–C40: 1.6282(19

Manganese-catalyzed C–C and C–N bond formation with alcohols via borrowing hydrogen or hydrogen auto-transfer

• Mohd Farhan Ansari,
• Atul Kumar Maurya,
• Abhishek Kumar and
• Saravanakumar Elangovan

Beilstein J. Org. Chem. 2024, 20, 1111–1166, doi:10.3762/bjoc.20.98

• products (Scheme 5). Interestingly, the dearomatized intermediate resulting from the reaction of base and Mn3 was isolated and characterized by X-ray analysis during the mechanistic investigation. In 2018, Kempe et al. disclosed that the choice of the base plays a critical role in the BH method for the

Mild and efficient synthesis and base-promoted rearrangement of novel isoxazolo[4,5-b]pyridines

• Vladislav V. Nikol’skiy,
• Mikhail E. Minyaev,
• Maxim A. Bastrakov and
• Alexey M. Starosotnikov

Beilstein J. Org. Chem. 2024, 20, 1069–1075, doi:10.3762/bjoc.20.94

• inhibitor of homeodomain-interacting protein kinases (HIPKs) [32], and combretastatin A-4 analogs evaluated for their anticancer properties against a panel of 60 human cancer cell lines [33] (Figure 2). The structures of all new compounds were confirmed by 1H and 13C NMR and HRMS. X-ray diffraction studies

• -oriented heterocyclic systems. Some examples of biologically active isoxazolo[4,5-b]pyridines with antibacterial [8], anticancer [12] and cytotoxic [10][13] acitivities. Biologically active analogs of compounds 13. X-ray crystal structures of compounds 12c (top left; the second crystallographically unique

• . Yields of compounds 12 and 13. Supporting Information Supporting Information File 16: Experimental section, NMR spectra and X-ray analysis data.

Structure–property relationships in dicyanopyrazinoquinoxalines and their hydrogen-bonding-capable dihydropyrazinoquinoxalinedione derivatives

• Tural N. Akhmedov,
• Ajeet Kumar,
• Daken J. Starkenburg,
• Kyle J. Chesney,
• Khalil A. Abboud,
• Novruz G. Akhmedov,
• Jiangeng Xue and
• Ronald K. Castellano

Beilstein J. Org. Chem. 2024, 20, 1037–1052, doi:10.3762/bjoc.20.92

• ). Single crystal X-ray diffraction data could be obtained for three DPQDs. One reveals pairwise hydrogen bonding in the solid state as well as a herringbone packing arrangement rendering it a promising candidate for additional studies in the context of organic optoelectronic devices. Keywords: conjugated

• moderate to excellent hole transport mobilities (1.5 × 10−3 and 1.5 cm2/Vs, respectively) [21]. In 2012, Miao et al. reported an H-bonding capable 1,4-dihydropyrazinopyrazine fragment within N-heteroacenes [22]. The X-ray analysis of single crystals revealed the formation of highly-ordered ribbons

• exhibits a noteworthy impact on the thermal stabilities (analyzed by TGA) of the compounds. The single-crystal X-ray diffraction of DPQD 2b exhibits a desirable herringbone solid-state arrangement for a potential OFET application. Complementary gas-phase computational analysis has provided insight into the

Novel analogues of a nonnucleoside SARS-CoV-2 RdRp inhibitor as potential antivirotics

• Luca Julianna Tóth,
• Kateřina Krejčová,
• Milan Dejmek,
• Eva Žilecká,
• Blanka Klepetářová,
• Lenka Poštová Slavětínská,
• Evžen Bouřa and
• Radim Nencka

Beilstein J. Org. Chem. 2024, 20, 1029–1036, doi:10.3762/bjoc.20.91

• insufficient evidence provided even by meticulous NMR analysis and eventually had to be confirmed by X-ray crystallography (Figure S1, Supporting Information File 1). Changing the ester function from an ethyl to an allyl group enabled a very mild cleavage using a Pd-mediated reaction with triethylsilane [28

• : Experimental procedures, spectra and X-ray data. Acknowledgements We thank Lucie Bednárová from the Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences for the help with the analysis of compound 13. Funding The work was supported by the National Institute of Virology and

Spin and charge interactions between nanographene host and ferrocene

• Akira Suzuki,
• Yuya Miyake,
• Ryoga Shibata and
• Kazuyuki Takai

Beilstein J. Org. Chem. 2024, 20, 1011–1019, doi:10.3762/bjoc.20.89

• (SQUID) [21][22] and X-ray magnetic circular dichroism (XMCD) spectroscopy [23]. However, only a tiny paramagnetic behavior of encapsulated ferrocene was observed, and no magnetic host–guest interactions were reported due to the diamagnetic nature of CNTs. Activated carbon fibers (ACFs) consist of a

• magnetic interactions between the nanographene host and FeCp2 guest molecules to achieve a ferromagnet using nanographene host–guest systems. In this study, we introduced ferrocene to ACFs and investigated the magnetic interaction between the host ACFs and ferrocene as magnetic guest molecule using X-ray

• surface of ACFs, which were removed by heating the FeCp2-treated ACFs at 150 °C for 3 hours without FeCp2 vapor. XPS spectra were recorded using a PHI-5600 (ULVAC-PHI) with an Al Kα X-ray source (1486.7 eV) for samples mounted on an indium film. Raman spectroscopy measurements were performed by LabRAM HR

Monitoring carbohydrate 3D structure quality with the Privateer database

• Jordan S. Dialpuri,
• Haroldas Bagdonas,
• Lucy C. Schofield,
• Phuong Thao Pham,
• Lou Holland and
• Jon Agirre

Beilstein J. Org. Chem. 2024, 20, 931–939, doi:10.3762/bjoc.20.83

• complement the growing glycan content of the PDB. Keywords: carbohydrates; database; N-glycans; N-glycosylation; polysaccharides; validation; website; Introduction Carbohydrate modelling is an important but often cumbersome stage in the macromolecular X-ray structure solution workflow. The accurate

One-pot Ugi-azide and Heck reactions for the synthesis of heterocyclic systems containing tetrazole and 1,2,3,4-tetrahydroisoquinoline

• Jiawei Niu,
• Yuhui Wang,
• Shenghu Yan,
• Yue Zhang,
• Xiaoming Ma,
• Qiang Zhang and
• Wei Zhang

Beilstein J. Org. Chem. 2024, 20, 912–920, doi:10.3762/bjoc.20.81

• and 13C NMR, and HRMS analysis. In addition, single crystals of compound 6d and 8c were obtained for X-ray analysis to confirm the structures (Figure 2). Conclusion In conclusion, we have developed a one-pot synthesis with two or three steps for making tetrazolo-pyrazino[2,1-a]isoquinolin-6(5H)-ones

Synthesis and properties of 6-alkynyl-5-aryluracils

• Ruben Manuel Figueira de Abreu,
• Till Brockmann,
• Alexander Villinger,
• Peter Ehlers and
• Peter Langer

Beilstein J. Org. Chem. 2024, 20, 898–911, doi:10.3762/bjoc.20.80

• ring instead of a benzene moiety. This was demonstrated by the introduction of thiophene (5r) and furan (5t) to the uracil structure. The molecules 5n and 5o could not be obtained, due to decomposition during the reaction. The structure of 5a was confirmed by X-ray crystallographic analysis. Crystals

• ). Samples were ionized by electron impact ionization (EI) on an Agilent 6890/5973 or Agilent 7890/5977 GC–MS equipped with a HP-5 capillary column using helium carrier gas or by electron spray ionization (ESI) on an Agilent 1200/6210 time-of-flight (TOF) LC–MS. X-ray single-crystal structure analysis was

• molecules within and between a layer with two molecules at the top and the bottom of the unit cell. b) Determined from X-ray structural analysis at 123 K. Element color: carbon (grey), hydrogen (white), oxygen (red) and nitrogen (blue). The thermal ellipsoids are drawn at the 50% probability level. UV–vis

(Bio)isosteres of ortho- and meta-substituted benzenes

• H. Erik Diepers and
• Johannes C. L. Walker

Beilstein J. Org. Chem. 2024, 20, 859–890, doi:10.3762/bjoc.20.78

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

• Abstract We confirm the previously revised stereochemistry of spiroviolene by X-ray crystallographically characterizing a hydrazone derivative of 9-oxospiroviolane, which is synthesized by hydroboration/oxidation of spiroviolene followed by oxidation of the resultant hydroxy group. An unexpected thermal

• , 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

• stereochemistry by X-ray crystallography using a hydrazone derivative of 1. Results and Discussion Our work commenced with the heterologous production of spiroviolene by E. coli using a recently developed isopentenol utilization pathway for the efficient supply of two C5 precursors for terpene biosynthesis

Skeletal rearrangement of 6,8-dioxabicyclo[3.2.1]octan-4-ols promoted by thionyl chloride or Appel conditions

• Martyn Jevric,
• Julian Klepp,
• Johannes Puschnig,
• Oscar Lamb,
• Christopher J. Sumby and
• Ben W. Greatrex

Beilstein J. Org. Chem. 2024, 20, 823–829, doi:10.3762/bjoc.20.74

• stereoisomer 10f in 91% yield. The selectivity of the NaBH4 reduction was confirmed for both 10d (see discussion in Supporting Information File 1) and 10e by X-ray crystallography (Figure 2 and Scheme 1, respectively). The oxygen-migration reaction giving 11a was initially observed using the readily available

• , with the exo-hemiacetals favoured due to steric interactions between the substituents and alcohol, while the attempted preparation of 12b led only to complex mixtures (Scheme 2). The products of the reactions were characterised by 1D and 2D NMR, and X-ray crystallography of members from each class was

• the X-ray crystal structures for 11a and 11b allowing for the unambiguous assignment of configuration. The chlorinated product 14 contaminating 11b exhibited a 1H NMR spectrum similar to the starting material 10b, except that the resonance for the H4 methine was shifted from δ 3.60 in 10b to δ 3.90

Advancements in hydrochlorination of alkenes

• Daniel S. Müller

Beilstein J. Org. Chem. 2024, 20, 787–814, doi:10.3762/bjoc.20.72

• forms a dissociated hydrogen chloride aggregate in the form of complexes 103 or 105. An X-ray structure of complex 105 was reported and the reaction 104 → 105 is described in the report by Snyder, though not stoichiometric balanced. These complexes seem to play a pivotal role in the hydrochlorination

Regioselective quinazoline C2 modifications through the azide–tetrazole tautomeric equilibrium

• Dāgs Dāvis Līpiņš,
• Andris Jeminejs,
• Una Ušacka,
• Anatoly Mishnev,
• Māris Turks and
• Irina Novosjolova

Beilstein J. Org. Chem. 2024, 20, 675–683, doi:10.3762/bjoc.20.61

• of 4-azido-6,7-dimethoxy-2-sulfonylquinazoline derivatives 12 were proven by chemical synthesis of the regioisomers 15 (Scheme 7) and X-ray analysis of 12a (Scheme 6). 6,7-Dimethoxy-2,4-diazidoquinazoline (13) was synthesized from commercially available dichloroquinazoline 7 in 93% yield. Further

• explanation for the present tetrazole form in the solutions. Surprisingly, FTIR and X-ray analyses of 12a in the solid state indicated the existence of 12a in the azide form. In subsequent experiments it was discovered that for less nucleophilic N-nucleophiles (piperidine, morpholine, N-methylpiperazine) C2

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

• -5′ desmethyl form of the product from the K187A variant of AdrI, which was created during the in-depth functional analysis of terpene cyclases involved in DMOA-derived meroterpenoid biosynthesis [21], through NMR and single-crystal X-ray crystallographic analyses (Figure 2C and Figure S1 in

• . 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

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

Recent developments in the engineered biosynthesis of fungal meroterpenoids

• Zhiyang Quan and
• Takayoshi Awakawa

Beilstein J. Org. Chem. 2024, 20, 578–588, doi:10.3762/bjoc.20.50

• mutagenesis of key enzymes, including terpene cyclases and α-ketoglutarate (αKG)-dependent dioxygenases, that contribute to the structural diversity. Notable progress in genome sequencing has led to the discovery of many novel genes encoding these enzymes, while continued efforts in X-ray crystallographic

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

• the reaction in the presence of DIPEA proceeded selectively, albeit more slowly. By increasing the DIPEA loading to 50 mol %, the product 2a was isolated in 75% yield after incubation for 7 days at room temperature. The structure of the obtained spirobutenolide was confirmed by single crystal X-ray

• of compound 4b has been confirmed by single crystal X-ray data. The next step was to investigate the possibility of obtaining six-membered oxygen-containing spiroheterocycles by interaction of DAS 1 with 2-(bromomethyl)benzyl alcohol (15) (Scheme 6). The synthesis was carried out under the conditions

• . These data are provided free of charge by the joint Cambridge Crystallographic Data Centre and Fachinformationszentrum Karlsruhe Access Structures service https://www.ccdc.cam.ac.uk/structures. Supporting Information File 30: General experimental information, X-ray crystallographic data, synthetic

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

Synthesis and biological profile of 2,3-dihydro[1,3]thiazolo[4,5-b]pyridines, a novel class of acyl-ACP thioesterase inhibitors

• Jens Frackenpohl,
• David M. Barber,
• Guido Bojack,
• Birgit Bollenbach-Wahl,
• Ralf Braun,
• Rahel Getachew,
• Sabine Hohmann,
• Kwang-Yoon Ko,
• Karoline Kurowski,
• Bernd Laber,
• Rebecca L. Mattison,
• Thomas Müller,
• Anna M. Reingruber,
• Dirk Schmutzler and
• Andrea Svejda

Beilstein J. Org. Chem. 2024, 20, 540–551, doi:10.3762/bjoc.20.46

• lead structure with ample space for structural variations. By formally replacing one pyridine moiety of 1,8-naphthyridine 4 by a five-membered thiazole unit, we have identified thiazolo[4,5-b]pyridine 5 as a strong inhibitor of acyl-ACP thioesterase, which has further been confirmed via an X-ray co

Ligand effects, solvent cooperation, and large kinetic solvent deuterium isotope effects in gold(I)-catalyzed intramolecular alkene hydroamination

• Ruichen Lan,
• Brock Yager,
• Yoonsun Jee,
• Cynthia S. Day and
• Amanda C. Jones

Beilstein J. Org. Chem. 2024, 20, 479–496, doi:10.3762/bjoc.20.43

• doublets at 107 and 69 ppm, with J = 275.5 Hz, and a singlet at 70.5 ppm (Figure 4c) [42]. In all attempts to prepare bisphos 7a, the singlet and set of doublets were observed, and always in the same approximate ratio. X-ray crystallographic analysis shows C2 rotational symmetry and confirms the identity