Electrochemical and spectroscopic properties of twisted dibenzo[g,p]chrysene derivatives

• Tomoya Imai,
• Ryuhei Akasaka,
• Naruhiro Yoshida,
• Toru Amaya and
• Tetsuo Iwasawa

Beilstein J. Org. Chem. 2022, 18, 963–971, doi:10.3762/bjoc.18.96

• design of DBC-based materials. Here, the electrochemical and spectroscopic properties of DBC derivatives were investigated, and the effects of substituents and torsion of the naphthalene moiety were examined based on density functional theory (DFT) calculations. All the substituted DBC derivatives showed

Electroreductive coupling of 2-acylbenzoates with α,β-unsaturated carbonyl compounds: density functional theory study on product selectivity

• Naoki Kise and
• Toshihiko Sakurai

Beilstein J. Org. Chem. 2022, 18, 956–962, doi:10.3762/bjoc.18.95

• 2 and subsequent rearrangement to 3 are also discussed. In particular, the latter mechanism was studied using density functional theory (DFT) calculations and it was suggested that the ΔG for the cyclization step of an intermediate enolate anion determines the product selectivity. Results and

Introducing a new 7-ring fused diindenone-dithieno[3,2-b:2',3'-d]thiophene unit as a promising component for organic semiconductor materials

• Valentin H. K. Fell,
• Joseph Cameron,
• Alexander L. Kanibolotsky,
• Eman J. Hussien and
• Peter J. Skabara

Beilstein J. Org. Chem. 2022, 18, 944–955, doi:10.3762/bjoc.18.94

• highly delocalised bipolaron states [69]. Computation of structure Since all attempts to grow crystals of EtH-T-DI-DTT failed, we predicted the structure with a density functional theory (DFT) gas-phase optimisation using the B3LYP[70][71]/6-311g(d,p) [72] level of theory, using both the Gaussian09 [73

Post-synthesis from Lewis acid–base interaction: an alternative way to generate light and harvest triplet excitons

• Hengjia Liu and
• Guohua Xie

Beilstein J. Org. Chem. 2022, 18, 825–836, doi:10.3762/bjoc.18.83

• the excited states, accounting for the decrease of band gap [27][37][43]. In 2018, Li et al. used density functional theory (DFT) to investigate the energy levels of polymers 19 (P1) and 20 (P2, Figure 10) containing pyrazine groups before and after the addition of B(C6F5)3 (see Figure 11a) [45

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

• using density functional theory (DFT) methods at the M11/cc-pVDZ level of theory. The cycloaddition reactions have been found to be HOMOcyclopropene–LUMOylide controlled while the transition-state energies for the reaction of 3-methyl-3-phenylcyclopropene with PRP are fully consistent with the

BINOL as a chiral element in mechanically interlocked molecules

• Matthias Krajnc and
• Jochen Niemeyer

Beilstein J. Org. Chem. 2022, 18, 508–523, doi:10.3762/bjoc.18.53

• catalysts ((S)-48/(S)-49, see Figure 13) for a broad range of substrates. While the bifunctional catenane (S,S)-47 delivers enantioselectivities between 84–98% ee, the monophosphoric acids (S)-48 and (S)-49 gave lower enantiomeric excesses (12–70% ee for (S)-48 and 9–84% ee for (S)-49). Density functional

• theory (DFT) studies suggested that the excellent stereoselectivities of the catenane are a direct result of the cooperative interaction of both phosphoric acid groups, enabled by the mechanical bond. Follow-up studies showed that such acid–acid interactions are also relevant for monophosphoric acid

Comparative study of thermally activated delayed fluorescent properties of donor–acceptor and donor–acceptor–donor architectures based on phenoxazine and dibenzo[a,j]phenazine

• Saika Izumi,
• Prasannamani Govindharaj,
• Anna Drewniak,
• Paola Zimmermann Crocomo,
• Satoshi Minakata,
• Leonardo Evaristo de Sousa,
• Piotr de Silva,
• Przemyslaw Data and
• Youhei Takeda

Beilstein J. Org. Chem. 2022, 18, 459–468, doi:10.3762/bjoc.18.48

• the efficacy of introducing two electronic donors on the acceptor unit. The calculations employed density functional theory (DFT) with the long-range corrected ωPBE functional and the 6-31G(d,p) basis set. Tuning of the range separation parameter was performed for both molecules [20] with the results

Iridium-catalyzed hydroacylation reactions of C1-substituted oxabenzonorbornadienes with salicylaldehyde: an experimental and computational study

• Angel Ho,
• Austin Pounder,
• Krish Valluru,
• Leanne D. Chen and
• William Tam

Beilstein J. Org. Chem. 2022, 18, 251–261, doi:10.3762/bjoc.18.30

• electron-withdrawing groups inactivates the iridium catalyst, perhaps by chelation with the carbonyl and the bridging oxygen atom. Computational Computational details All density functional theory (DFT) calculations in this study were carried out with the Gaussian 16, C.01 suite of programs [68]. Geometry

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

• -functional theory (DFT) computations were used to explain the reaction mechanism for the ring opening of the epoxide and the formation of five-membered lactones. The stereochemistry of the synthesized compounds was determined by 1D and 2D NMR spectroscopy. The configuration of methyl 6-hydroxy-9-oxo-8

• -en-10-one is described. cis-9-Azabicyclo[6.2.0]dec-6-en-10-one was transformed into the corresponding amino ester and its protected amine. Oxidation of the double bond in the N-Boc-protected methyl 2-aminocyclooct-3-ene-1-carboxylate then delivered the targeted amino acid and its derivatives. Density

Peptide stapling by late-stage Suzuki–Miyaura cross-coupling

• Hendrik Gruß,
• Rebecca C. Feiner,
• Ridhiwan Mseya,
• David C. Schröder,
• Michał Jewgiński,
• Kristian M. Müller,
• Rafał Latajka,
• Antoine Marion and
• Norbert Sewald

Beilstein J. Org. Chem. 2022, 18, 1–12, doi:10.3762/bjoc.18.1

• -helicity in water. Investigation of several derivatives by means of density functional theory (DFT) geometry optimisations indicated that substitution at indole C6 tends to induce more significant deformation of the peptide chain compared to substitution at indole C7. Moreover, introduction of an

Effect of a twin-emitter design strategy on a previously reported thermally activated delayed fluorescence organic light-emitting diode

• Ettore Crovini,
• Zhen Zhang,
• Yu Kusakabe,
• Yongxia Ren,
• Yoshimasa Wada,
• Bilal A. Naqvi,
• Prakhar Sahay,
• Tomas Matulaitis,
• Stefan Diesing,
• Ifor D. W. Samuel,
• Wolfgang Brütting,
• Katsuaki Suzuki,
• Hironori Kaji,
• Stefan Bräse and
• Eli Zysman-Colman

Beilstein J. Org. Chem. 2021, 17, 2894–2905, doi:10.3762/bjoc.17.197

• DICzTRZ were determined by a combination of NMR spectroscopy, mass spectrometry, and IR spectroscopy. Theoretical calculations Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations in the gas phase at the PBE0/6-31G(d,p) level reveal the potential of DICzTRZ as a TADF material. The

Iron-catalyzed domino coupling reactions of π-systems

• Austin Pounder and
• William Tam

Beilstein J. Org. Chem. 2021, 17, 2848–2893, doi:10.3762/bjoc.17.196

• provided the desired carboamination product 164. By using methyl cinnamate derivatives, the reactions were highly diastereoselective for the formation of 1,2-anti carboamination products. Notably, the Ritter reaction was found to be the origin of diastereoselectivity on the basis of a density functional

• theory (DFT) mechanistic study. The authors proposed a radical-polar crossover mechanism. First, a SET from Fe(II) to the alkyl diacyl peroxide generates the alkyl acyloxy radical which decarboxylates to afford the alkyl radical 165. Addition of the radical across the alkene affords the benzylic radical

Synthesis and investigation on optical and electrochemical properties of 2,4-diaryl-9-chloro-5,6,7,8-tetrahydroacridines

• Najeh Tka,
• Mohamed Adnene Hadj Ayed,
• Mourad Ben Braiek,
• Mahjoub Jabli and
• Peter Langer

Beilstein J. Org. Chem. 2021, 17, 2450–2461, doi:10.3762/bjoc.17.162

• a PGSTAT30 Autolab potentiostat. Theoretical calculations The theoretical studies were realized in vacuum with the Gaussian 09 program [70]. The geometry of the equilibrium conformer at the ground state was first found at AM1 level. Then, further optimization through density functional theory (DFT

Nomimicins B–D, new tetronate-class polyketides from a marine-derived actinomycete of the genus Actinomadura

• Zhiwei Zhang,
• Tao Zhou,
• Taehui Yang,
• Keisuke Fukaya,
• Enjuro Harunari,
• Shun Saito,
• Katsuhisa Yamada,
• Chiaki Imada,
• Daisuke Urabe and
• Yasuhiro Igarashi

Beilstein J. Org. Chem. 2021, 17, 2194–2202, doi:10.3762/bjoc.17.141

• functional theory (DFT) calculation of the ECD spectrum for 4, for which the absolute configuration was established by the modified Mosher’s method in our previous work [15]. Since the acyltetronic acid exists as a mixture of keto–enol tautomers, the calculation was carried out using the four possible

• (Table S1, Supporting Information File 1) and 3JHH coupling constants [15]. The absolute configuration of 1 was deduced to be the same as 4 in consideration of the overall similarity of the electronic circular dichroism (ECD) spectra of 1 and 4 (Figure 4). This proposition was evidenced by the density

Electron-rich triarylphosphines as nucleophilic catalysts for oxa-Michael reactions

• Susanne M. Fischer,
• Simon Renner,
• A. Daniel Boese and
• Christian Slugovc

Beilstein J. Org. Chem. 2021, 17, 1689–1697, doi:10.3762/bjoc.17.117

• radical cations of the phosphines under investigation were calculated by density functional theory (DFT), namely B3LYP-def2-TZVPPD. According to criterion introduced by Stewart et al. postulating air stability of phosphines when the SOMO energy is higher than −10 eV, the three derivatives should be air

2,4-Bis(arylethynyl)-9-chloro-5,6,7,8-tetrahydroacridines: synthesis and photophysical properties

• Najeh Tka,
• Mohamed Adnene Hadj Ayed,
• Mourad Ben Braiek,
• Mahjoub Jabli,
• Noureddine Chaaben,
• Kamel Alimi,
• Stefan Jopp and
• Peter Langer

Beilstein J. Org. Chem. 2021, 17, 1629–1640, doi:10.3762/bjoc.17.115

• molecules have been examined. Additionally, theoretical studies based on density functional theory (DFT/B3LYP/6-31G(d)) were carried out. Keywords: alkynes; catalysis; cross-coupling; heterocycles; palladium; Introduction The development and design of small π-conjugated molecules have attracted increasing

• . In order to elucidate these experimental observations, quantum chemical calculations based on density functional theory (DFT) methodology were performed. The estimated visualization of highest occupied and lowest unoccupied molecular orbitals, as well as the molecular electrostatic potential (MEP) of

• equilibrium conformer at ground state was first found at AM1 level. Then, further optimizations through density functional theory (DFT) approach [73] at the restricted Becke3–Lee–Yang–Parr hybrid functional (B3LYP) with standard basis set 6-31G were carried out. Experimental procedure and spectroscopic data

Double-headed nucleosides: Synthesis and applications

• Vineet Verma,
• Jyotirmoy Maity,
• Vipin K. Maikhuri,
• Ritika Sharma,
• Himal K. Ganguly and
• Ashok K. Prasad

Beilstein J. Org. Chem. 2021, 17, 1392–1439, doi:10.3762/bjoc.17.98

Structural effects of meso-halogenation on porphyrins

• Keith J. Flanagan,
• Maximilian Paradiz Dominguez,
• Zoi Melissari,
• Hans-Georg Eckhardt,
• René M. Williams,
• Dáire Gibbons,
• Caroline Prior,
• Gemma M. Locke,
• Alina Meindl,
• Aoife A. Ryan and
• Mathias O. Senge

Beilstein J. Org. Chem. 2021, 17, 1149–1170, doi:10.3762/bjoc.17.88

• formation of the crystal networks. This is complemented with the use of density functional theory (DFT) calculation of structures that have currently not been determined due to difficulties of obtained crystals of sufficient quality for X-ray determination. Additionally, DFT calculations were conducted for

Prins cyclization-mediated stereoselective synthesis of tetrahydropyrans and dihydropyrans: an inspection of twenty years

• Asha Budakoti,
• Pradip Kumar Mondal,
• Prachi Verma and
• Jagadish Khamrai

Beilstein J. Org. Chem. 2021, 17, 932–963, doi:10.3762/bjoc.17.77

• and co-workers explained the formation of all-cis-2,4,6-trisubstituted THPs with the help of density functional theory (DFT) and stated that in the presence of an external nucleophile, the stabilization of the carbocation intermediate is favored through hyperconjugation [28]. The vacant p-orbital of

Synthesis, structural characterization, and optical properties of benzo[f]naphtho[2,3-b]phosphoindoles

• Mio Matsumura,
• Takahiro Teramoto,
• Masato Kawakubo,
• Masatoshi Kawahata,
• Yuki Murata,
• Kentaro Yamaguchi,
• Masanobu Uchiyama and
• Shuji Yasuike

Beilstein J. Org. Chem. 2021, 17, 671–677, doi:10.3762/bjoc.17.56

• ]. Unfortunately, the electrochemistry of some compounds could not be determined under the conditions available to us. Therefore, computational investigations are particularly useful for understanding the trends of the electrochemical and photophysical properties of molecular materials. Density functional theory

• (DFT) calculations [27] were performed at the B3LYP/LanL2DZ level of theory to gain additional understanding of the electronic structures. The HOMO and LUMO energies of the selected compounds are listed in Table 3. The DFT calculations showed that these compounds have HOMO–LUMO gaps of 3.60–3.96 eV

Mesoionic tetrazolium-5-aminides: Synthesis, molecular and crystal structures, UV–vis spectra, and DFT calculations

• Vladislav A. Budevich,
• Sergei V. Voitekhovich,
• Alexander V. Zuraev,
• Vadim E. Matulis,
• Vitaly E. Matulis,
• Alexander S. Lyakhov,
• Ludmila S. Ivashkevich and
• Oleg A. Ivashkevich

Beilstein J. Org. Chem. 2021, 17, 385–395, doi:10.3762/bjoc.17.34

• structures are known [17][28]. Thus, the information on tetrazole-5-aminides is very limited and fragmentary. In the present work, we try to fill this gap by carrying out experimental (synthesis, X-ray, UV–vis) and theoretical density functional theory (DFT) studies of some selected 1,3-dialkyltetrazolium-5

Exploring the possibility of using fluorine-involved non-conjugated electron-withdrawing groups for thermally activated delayed fluorescence emitters by TD-DFT calculation

• Dongyang Chen and
• Eli Zysman-Colman

Beilstein J. Org. Chem. 2021, 17, 210–223, doi:10.3762/bjoc.17.21

• [28][29]. Results and Discussion We employed density functional theory (DFT) and TD-DFT calculations to predict the photophysical properties of these emitters in order to assess their potential as TADF emitters for OLEDs. All ground-state calculations were performed using PBE0/6-31G(d,p) in the gas

UV resonance Raman spectroscopy of the supramolecular ligand guanidiniocarbonyl indole (GCI) with 244 nm laser excitation

• Tim Holtum,
• Vikas Kumar,
• Daniel Sebena,
• Jens Voskuhl and
• Sebastian Schlücker

Beilstein J. Org. Chem. 2020, 16, 2911–2919, doi:10.3762/bjoc.16.240

• the results from density functional theory (DFT) calculations. Keywords: GCI; GCP; guanidiniocarbonyl indole; guanidiniocarbonyl pyrrole; UVRR; Raman spectroscopy; resonance Raman; Introduction Supramolecular ligands are capable to selectively bind to peptides and proteins via reversible non

• the results from density functional theory (DFT) calculations. The assignment of the peaks detectable in the experimental UVRR spectrum is mainly based on the experimental wavenumber position (peak position). Only normal modes with non-vanishing Raman activities were considered. One cannot expect an

Fluorine effect in nucleophilic fluorination at C4 of 1,6-anhydro-2,3-dideoxy-2,3-difluoro-β-D-hexopyranose

• Danny Lainé,
• Vincent Denavit,
• Olivier Lessard,
• Laurie Carrier,
• Charles-Émile Fecteau,
• Paul A. Johnson and
• Denis Giguère

Beilstein J. Org. Chem. 2020, 16, 2880–2887, doi:10.3762/bjoc.16.237

• density functional theory (DFT) calculations). Finally, we wish to report the preparation of novel multi-vicinal fluorinated alditol analogues using a simple reduction protocol. Results and Discussion We initially supposed that DAST, a commonly used reagent to install fluorine atoms on the carbohydrate

Synthesis of 4-substituted azopyridine-functionalized Ni(II)-porphyrins as molecular spin switches

• Jannis Ludwig,
• Tobias Moje,
• Fynn Röhricht and
• Rainer Herges

Beilstein J. Org. Chem. 2020, 16, 2589–2597, doi:10.3762/bjoc.16.210

• is always in a high paramagnetic state (>80%) and showed only minor switching efficiency after irradiation (4%). This is attributed to intramolecular coordination of the trans state (Supporting Information File 1, Figure S17). Application of density functional theory (DFT) at the B3LYP/def2TZVP//PBE