Cyclodextrin-based rotaxanes for polymer materials: challenge on simultaneous realization of inexpensive production and defined structures

• Yosuke Akae

Beilstein J. Org. Chem. 2024, 20, 3026–3049, doi:10.3762/bjoc.20.252

Facile preparation of fluorine-containing 2,3-epoxypropanoates and their epoxy ring-opening reactions with various nucleophiles

• Yutaro Miyashita,
• Sae Someya,
• Tomoko Kawasaki-Takasuka,
• Tomohiro Agou and
• Takashi Yamazaki

Beilstein J. Org. Chem. 2024, 20, 2421–2433, doi:10.3762/bjoc.20.206

• intramolecular interaction between fluorine and metals would also facilitate the smooth progress of these reactions. Such high potential of 1a allowed us to apply it to nucleophilic epoxidation because the resultant epoxyester 2a is recognized as an intriguing building block (Scheme 1). Another expectation to 2a

Oxidation of benzylic alcohols to carbonyls using N-heterocyclic stabilized λ³-iodanes

• Thomas J. Kuczmera,
• Pim Puylaert and
• Boris J. Nachtsheim

Beilstein J. Org. Chem. 2024, 20, 1677–1683, doi:10.3762/bjoc.20.149

• ]. A crystal structure was additionally obtained for tetrazine 1c. Bond lengths and angles were similar to those of known five-membered NHIs [25], including a strong intramolecular interaction between the nitrogen of the tetrazine and the hypervalent iodine atom (I1–N1: 2.44(4) Å; the sum of VdW radii

Stability trends in carbocation intermediates stemming from germacrene A and hedycaryol

• Naziha Tarannam,
• Prashant Kumar Gupta,
• Shani Zev and
• Dan Thomas Major

Beilstein J. Org. Chem. 2024, 20, 1189–1197, doi:10.3762/bjoc.20.101

• (Figure 2), we see that these carbocations are relatively more stable than in the case for F and H. The break in trend between germacrene A and hedycaryol carbocations is due to the nearby hydroxy group’s ability to stabilize carbocations (i.e., F-OH and H-OH). The effect of this intramolecular

• interaction is even more distinct when inspecting the electronic energies (Figure S1, Supporting Information File 1), where we observe a significant stabilizing effect of the hydroxyl–cation interaction for F-OH and H-OH. This is clearly discernible from the C+···OH distances (Figure 4, Table 1) and visible

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

• (Supporting Information File 1) and confirms they are in good accordance. For hdz-CH3, a maximum percentage error of 3% for bonds and 2% for angles was observed, while hdz-NO2 presented values of 2% and 3% for these parameters, respectively. In turn, the intramolecular interaction OH···N1 showed maximum

Exploring the role of halogen bonding in iodonium ylides: insights into unexpected reactivity and reaction control

• Carlee A. Montgomery and
• Graham K. Murphy

Beilstein J. Org. Chem. 2023, 19, 1171–1190, doi:10.3762/bjoc.19.86

• -hole bond is the non-covalent inter- or intramolecular interaction between the σ-hole of a group IV–VII atom with the electron-rich site of Lewis bases such as anions, hydrides, or even π electrons [24][30]. Halogen bonding is a subset of this bonding classification, represented by the generic bonding

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

• solvents, including water. The exciplex was formed by the intramolecular interaction of guanine and pyrene, linked by a flexible methylene chain [10]. Our lab has conducted considerable research on phenanthridine derivatives, and earlier research has demonstrated that two phenanthridine units can also

Conformational preferences of fluorine-containing agrochemicals and their implications for lipophilicity prediction

• Daniela Rodrigues Silva,
• Joyce K. Daré and
• Matheus P. Freitas

Beilstein J. Org. Chem. 2020, 16, 2469–2476, doi:10.3762/bjoc.16.200

• Juaristi and Notario [9], and O’Hagan and co-workers [10]. Besides, there is also an interaction between the fluorine electron lone pair nF and the σ*NH orbital of the amine group (of 3.2 kcal mol−1, see Table 1). Iga also experiences this stabilizing hydrogen bond-like intramolecular interaction (nF → σNH

Fluorohydration of alkynes via I(I)/I(III) catalysis

• Jessica Neufeld,
• Constantin G. Daniliuc and
• Ryan Gilmour

Beilstein J. Org. Chem. 2020, 16, 1627–1635, doi:10.3762/bjoc.16.135

• and 9, respectively, Figure 3A). Deletion of the ester carbonyl (10) and replacement of the phenyl group by methyl (11) was also detrimental. From these data it is tempting to speculate upon the involvement of a chair-like transition state in which the intramolecular interaction of the phenyl π-system

Synthesis of 4-(2-fluorophenyl)-7-methoxycoumarin: experimental and computational evidence for intramolecular and intermolecular C–F···H–C bonds

• Vuyisa Mzozoyana,
• Fanie R. van Heerden and
• Craig Grimmer

Beilstein J. Org. Chem. 2020, 16, 190–199, doi:10.3762/bjoc.16.22

• conditions via a three-step reaction. The solution-state 1H NMR spectra of 6 showed a strong intramolecular interaction between F and H5 (JFH = 2.6 Hz) and 13C NMR suggested that this C–F···H–C coupling is a through-space interaction. The 2D 19F-{1H} HOESY and 1H-{19F} 1D experiments were done to confirm

• -methoxycoumarin (6) via the Pechmann reaction was successful. The solution-state 1H and 13C NMR spectra of 6 showed that there is a strong intramolecular interaction between F and H5 (JFH = 2.6 Hz) and suggest that this interaction is through-space C–F···H–C coupling, since C5 is coupled to F (JFC = 1.4 Hz

Synthesis, liquid crystalline behaviour and structure–property relationships of 1,3-bis(5-substituted-1,3,4-oxadiazol-2-yl)benzenes

• Afef Mabrouki,
• Malek Fouzai,
• Armand Soldera,
• Abdelkader Kriaa and
• Ahmed Hedhli

Beilstein J. Org. Chem. 2020, 16, 149–158, doi:10.3762/bjoc.16.17

• electron D–A concept may be regarded as Lewis base–Lewis acid type or charge-transfer. Based upon the above considerations, we could attribute the close proximity of fluorinated chains in conformation B to a throw space electron D–A intramolecular interaction between the perfluoroalkyl chains (electron

1,2,3,4-Tetrahydro-1,4,5,8-tetraazaanthracene revisited: properties and structural evidence of aromaticity loss

• Arnault Heynderickx,
• Sébastien Nénon,
• Olivier Siri,
• Vladimir Lokshin and
• Vladimir Khodorkovsky

Beilstein J. Org. Chem. 2019, 15, 2059–2068, doi:10.3762/bjoc.15.203

• the benzene ring planarity as shown in Figure 1: the torsion angles C7–C6–C1–C14 and C7–C8–C13–C14 exceed 2 degrees. The planarity distortion cannot be attributed solely to the intramolecular interaction effects, as our calculations [22] using the B3LYP/6-311+G(2d,p)//B3LYP/6-311+G(2d,p) model

Adhesion, forces and the stability of interfaces

• Robin Guttmann,
• Johannes Hoja,
• Christoph Lechner,
• Reinhard J. Maurer and
• Alexander F. Sax

Beilstein J. Org. Chem. 2019, 15, 106–129, doi:10.3762/bjoc.15.12

Preparation and X-ray structure of 2-iodoxybenzenesulfonic acid (IBS) – a powerful hypervalent iodine(V) oxidant

• Irina A. Mironova,
• Pavel S. Postnikov,
• Rosa Y. Yusubova,
• Akira Yoshimura,
• Thomas Wirth,
• Viktor V. Zhdankin,
• Victor N. Nemykin and
• Mekhman S. Yusubov

Beilstein J. Org. Chem. 2018, 14, 1854–1858, doi:10.3762/bjoc.14.159

• )=O(2)···I(2) and ≈2.71 Å for I(4)=O(16)···I(2)) secondary contact with the I(2) center. In contrast, the third molecule of 6 has pentacoordinated iodine(V) center formed by two short I(3)=O bonds, one I–C bond, a relatively long (≈2.49 Å) I···OSO2 intramolecular interaction and a relatively long

Rh(II)-mediated domino [4 + 1]-annulation of α-cyanothioacetamides using diazoesters: A new entry for the synthesis of multisubstituted thiophenes

• Jury J. Medvedev,
• Ilya V. Efimov,
• Yuri M. Shafran,
• Vitaliy V. Suslonov,
• Vasiliy A. Bakulev and
• Valerij A. Nikolaev

Beilstein J. Org. Chem. 2017, 13, 2569–2576, doi:10.3762/bjoc.13.253

• examples of such reactions are for instance syntheses of multisubstituted indolines [23][24][25], pyrrolidines [26][27][28][29], dihydropyrroles [29], tetrahydrofurans [27][28], and 2,5-dihydrofurans [31][32], which proceed as intramolecular interaction of generated ammonium or oxonium ylides with carbonyl

Phosphonic acid: preparation and applications

• Charlotte M. Sevrain,
• Mathieu Berchel,
• Hélène Couthon and
• Paul-Alain Jaffrès

Beilstein J. Org. Chem. 2017, 13, 2186–2213, doi:10.3762/bjoc.13.219

• produce compound 98 [213] (Figure 28A). A second example corresponds to the nucleophilic addition of N-heterocyclic phosphine 99 to a nitroalkene (phospho-Michael reaction) as shown in Figure 28B. The thiourea unit in 99 plays a crucial role by assuming intramolecular interaction with the nitro function

Molecular-level architectural design using benzothiadiazole-based polymers for photovoltaic applications

• Vinila N. Viswanathan,
• Arun D. Rao,
• Upendra K. Pandey,
• Arul Varman Kesavan and
• Praveen C. Ramamurthy

Beilstein J. Org. Chem. 2017, 13, 863–873, doi:10.3762/bjoc.13.87

• on the optoelectronics and photovoltaic performances has been demonstrated. It was observed that the incorporation of fluorine, a strong electron-withdrawing group, resulted in deeper HOMO energy levels for the polymer P2 as compared to polymer P1. The fluorination also enhances the intramolecular

• interaction between the polymer chains, which is reflected in the higher hole mobility of P2 over P1. Though the photovoltaic parameter values are very low for these polymers, it was observed that fluorination could increase the overall device performance by ≈110%. The effect of increased planarity along the

Experimental and theoretical insights in the alkene–arene intramolecular π-stacking interaction

• Valeria Corne,
• Ariel M. Sarotti,
• Carmen Ramirez de Arellano,
• Rolando A. Spanevello and
• Alejandra G. Suárez

Beilstein J. Org. Chem. 2016, 12, 1616–1623, doi:10.3762/bjoc.12.158

• reported the synthesis of a novel chiral auxiliary that demonstrated to be very efficient in an asymmetric Diels–Alder reaction between the acrylic ester derivative and cyclopentadiene [16]. The facial selectivity of this reaction proved to be due to an aryl–vinyl π-stacking intramolecular interaction that

• , spectroscopic and computational evidence of the structurally related chiral acrylates to get new insights into the alkene–arene intramolecular interaction. Besides, it was evaluated the effect of the electron density of the aromatic counterpart and its influence on the asymmetric inductive capacity of the

• − Egauche) can be seen as a measurement of the stabilization caused by the intramolecular interaction. The ΔEag values computed for all acrylate derivatives 6 show that ΔEag for acrylate 6a is higher than that for 6b and 6c (3.91 kcal/mol vs 3.49 kcal/mol vs 3.27 kcal/mol, respectively), suggesting a

cis–trans-Amide isomerism of the 3,4-dehydroproline residue, the ‘unpuckered’ proline

• Vladimir Kubyshkin and
• Nediljko Budisa

Beilstein J. Org. Chem. 2016, 12, 589–593, doi:10.3762/bjoc.12.57

• electrophilicity of the terminal carbonyl groups (as seen previously in Ac-Xaa acidity) does not have a significant impact on the intramolecular interaction between the two carbonyl groups (as seen from Ks-trans/s-cis values). Similarly, Jenkins et al. reported on bicyclic proline analogues and demonstrated that

New synthetic strategies for xanthene-dye-appended cyclodextrins

• Milo Malanga,
• Andras Darcsi,
• Mihaly Balint,
• Gabor Benkovics,
• Tamas Sohajda and
• Szabolcs Beni

Beilstein J. Org. Chem. 2016, 12, 537–548, doi:10.3762/bjoc.12.53

• primary rim of the CD. The plane of the xanthene moiety of the fluorophore should be twisted above the primary side of the CD in a way that H8 would be the only point of (intramolecular) interaction with the upper rim of the CD cavity. To summarize, the compound Flu-β-CD was obtained in high purity and

Investigation of the role of stereoelectronic effects in the conformation of piperidones by NMR spectroscopy and X-ray diffraction

• Cesar Garcias-Morales,
• David Ortegón-Reyna and
• Armando Ariza-Castolo

Beilstein J. Org. Chem. 2015, 11, 1973–1984, doi:10.3762/bjoc.11.213

• rings on the six-membered ring with the boat conformation are antiperiplanar to the aromatic ring on the six-membered ring with the chair conformation (Figure 7a). This geometry allowed a C–H∙∙∙π intramolecular interaction between the aromatic rings. There are also C–H∙∙∙π intermolecular interactions

Star-shaped tetrathiafulvalene oligomers towards the construction of conducting supramolecular assembly

• Masahiko Iyoda and
• Masashi Hasegawa

Beilstein J. Org. Chem. 2015, 11, 1596–1613, doi:10.3762/bjoc.11.175

• of 16•+, 17•+, and 18•+ show intramolecular interaction between TTF and TTF•+, and the absorption maxima were observed at ca. 450 and 750 nm, together with broad absorption of intramolecular CT interactions between two TTF units at 1400, 1300, 1200 nm, respectively. The magnitude of these broad

Glycoluril–tetrathiafulvalene molecular clips: on the influence of electronic and spatial properties for binding neutral accepting guests

• Yoann Cotelle,
• Marie Hardouin-Lerouge,
• Stéphanie Legoupy,
• Olivier Alévêque,
• Eric Levillain and
• Piétrick Hudhomme

Beilstein J. Org. Chem. 2015, 11, 1023–1036, doi:10.3762/bjoc.11.115

• allow an intramolecular interaction to occur between two TTF units during the first oxidation step. In order to address this issue and to explore possible intermolecular (between two clips) interactions, concentration dependence electrochemical experiments were performed. Cyclic voltammograms were

Interactions between tetrathiafulvalene units in dimeric structures – the influence of cyclic cores

• Huixin Jiang,
• Virginia Mazzanti,
• Christian R. Parker,
• Søren Lindbæk Broman,
• Jens Heide Wallberg,
• Karol Lušpai,
• Adam Brincko,
• Henrik G. Kjaergaard,
• Anders Kadziola,
• Peter Rapta,
• Ole Hammerich and
• Mogens Brøndsted Nielsen

Beilstein J. Org. Chem. 2015, 11, 930–948, doi:10.3762/bjoc.11.104

• complex spectroelectrochemical responses may be explained by two possible mechanisms. The first one concerns an intramolecular interaction of two polaronic TTF units leading to the EPR silent polaron pair in the singlet state. The second possibility could be the formation of intermolecular π-dimers [28

• generated for the dication of both of these compounds, which signals intramolecular interaction of the two polaronic TTF units as we exclude π-dimerization since the EPR inactivity did not depend on the concentration of the species. A non-negligible interaction between the polaronic states was observed for

Cyclodextrin-grafted polymers functionalized with phosphanes: a new tool for aqueous organometallic catalysis

• Jonathan Potier,
• Stéphane Menuel,
• David Mathiron,
• Véronique Bonnet,
• Frédéric Hapiot and
• Eric Monflier

Beilstein J. Org. Chem. 2014, 10, 2642–2648, doi:10.3762/bjoc.10.276

• diffusion coefficients would have been observed otherwise. Similar behaviours were observed in D2O and CDCl3. Accordingly, the intramolecular interaction between the grafted phosphanes and the grafted CDs was not very strong as the recognition process between them could be easily displaced by a competitor