Dienophilic reactivity of 2-phosphaindolizines: a conceptual DFT investigation

• Nosheen Beig,
• Aarti Peswani and
• Raj Kumar Bansal

Beilstein J. Org. Chem. 2022, 18, 1217–1224, doi:10.3762/bjoc.18.127

• with DMB (Figure 3) [15]. The DFT based on the Hohenberg–Kohn theorems and later on the Kohn–Sham approximation made it possible to study the progress of organic reactions with manageable computational costs [16][17]. Parr and co-worker [18] developed “Conceptual DFT”, a subfield of DFT which allows to

• organophosphorus compounds. Computational Methods All calculations were done using the Gaussian 16 program [29]. We found that almost without exception, hybrid of Becke 3 and LYP correlation functional [30][31] has been used for determining reactivity descriptors [32][33][34][35] and the results were found to be

• >Y=P– functionality of 2-phosphaindolizines (dienophile). Supporting Information Supporting Information File 260: Cartesian coordinates of the geometries optimized (Table S1) at the B3LYP/6-31+G (d) level of theory. Acknowledgements The computational facilities provided by the IIS (deemed to be

Mechanochemical bottom-up synthesis of phosphorus-linked, heptazine-based carbon nitrides using sodium phosphide

• Blaine G. Fiss,
• Georgia Douglas,
• Michael Ferguson,
• Jorge Becerra,
• Jesus Valdez,
• Trong-On Do,
• Tomislav Friščić and
• Audrey Moores

Beilstein J. Org. Chem. 2022, 18, 1203–1209, doi:10.3762/bjoc.18.125

• constitutes the building block of g-CN, as opposed to in a linking position. Computational studies by Hartley and Martsinovich have investigated the influence of various linkers, including phosphorus atoms, on both the structure and optical behavior of heptazine-based graphitic carbon nitrides [3]. Yet

• -PCN300 material showed an up-field shift of all main resonances towards −14.4 ppm and −20.6 ppm (Figure 3b). As previously shown by our group [38], such a shift in main resonance positioning is indicative of the organization of the formed sheets, indicating a layered structure. Computational analysis The

• 31P NMR chemical shifts were calculated using the plane-wave density function theory (DFT) code CASTEP v20.11 (see Supporting Information File 1 for full computational details) [45]. In the absence of an experimentally resolved crystal structure for g-h-PCN, we followed a similar methodology to our

Thermally activated delayed fluorescence (TADF) emitters: sensing and boosting spin-flipping by aggregation

• Ashish Kumar Mazumdar,
• Gyana Prakash Nanda,
• Nisha Yadav,
• Upasana Deori,
• Upasha Acharyya,
• Bahadur Sk and
• Pachaiyappan Rajamalli

Beilstein J. Org. Chem. 2022, 18, 1177–1187, doi:10.3762/bjoc.18.122

• stronger molar extinction coefficient was obtained for the CT band in BPy-pTC (ε373 nm = 17310 M−1⋅cm−1) as compared to BPy-p3C (ε365 nm = 14690 M−1⋅cm−1). Computational calculations were performed to understand the ground state electronic communication between the donor and acceptor in BPy-pTC and BPy-p3C

• aggregates. Supporting Information Supporting Information File 204: General information, synthesis and characterization data including NMR spectra, computational details, UV–vis data, Lippert–Mataga plot, and acid–base switching. Funding A. K. M. is grateful to the Prime Minister's Research Fellowship

Experimental and theoretical studies on the synthesis of 1,4,5-trisubstituted pyrrolidine-2,3-diones

• Nguyen Tran Nguyen,
• Vo Viet Dai,
• Nguyen Ngoc Tri,
• Luc Van Meervelt,
• Nguyen Tien Trung and
• Wim Dehaen

Beilstein J. Org. Chem. 2022, 18, 1140–1153, doi:10.3762/bjoc.18.118

• Nguyen Tran Nguyen Vo Viet Dai Nguyen Ngoc Tri Luc Van Meervelt Nguyen Tien Trung Wim Dehaen Department of Chemistry, University of Science and Education, the University of Da Nang, Ton Duc Thang 459, 550000 Da Nang, Viet Nam Laboratory of Computational Chemistry and Modelling, Faculty of Natural

• proposed based on computational results and the main product is formed favorably following the PES via the lowest ΔG# pathway in both the gas-phase and an ethanol solvent model. DFT calculations showed that kinetic selectivity is more significant than thermodynamic selectivity for forming main products

• )ethylene-1,5-diphenylpyrrolidine-2,3-dione in the present work. To the best of our knowledge, it is the first time the reaction mechanism between 3-pyrrolin-2-one derivative and methylamine was explained in detail via computational studies. Results and Discussion A model reaction of benzaldehyde (1a

Enzymes in biosynthesis

• Jeroen S. Dickschat

Beilstein J. Org. Chem. 2022, 18, 1131–1132, doi:10.3762/bjoc.18.116

• novel products [7]. An alternative approach is offered by computational chemistry, which is ideally performed in combination with experimental verification of the computational results, e.g., through the enzymatic conversion of isotopically labelled compounds [8]. This thematic issue will cover all

A Streptomyces P450 enzyme dimerizes isoflavones from plants

• Run-Zhou Liu,
• Shanchong Chen and
• Lihan Zhang

Beilstein J. Org. Chem. 2022, 18, 1107–1115, doi:10.3762/bjoc.18.113

• compound for calculation of ABTS-reducing activity (in %). Computational ECD calculation of compound 1 Merck molecular force field (MMFF) and DFT as well as TDDFT calculations were carried out with the Spartan 14 software (Wavefunction Inc.) and the Gaussian 16 program [41], respectively. Conformers within

Understanding the competing pathways leading to hydropyrene and isoelisabethatriene

• Shani Zev,
• Marion Ringel,
• Ronja Driller,
• Bernhard Loll,
• Thomas Brück and
• Dan T. Major

Beilstein J. Org. Chem. 2022, 18, 972–978, doi:10.3762/bjoc.18.97

• on the mechanistic details of the HP and IE pathways using computational methods in the gas phase. Gas-phase studies have been crucial in understanding terpene chemistry [10][11][12][13][14][15][16][17][18][19][20][21][22]. This work sheds light on the thermodynamic and kinetic parameters of the

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

• optimized structures obtained based on the theoretical calculation. Acknowledgements The computation was performed using Research Center for Computational Science, Okazaki, Japan (Project: 21-IMS-C190, 22-IMS-C174). We thank Prof. Shinobu Aoyagi at Graduate School of Science, Nagoya City University for the

Anti-inflammatory aromadendrane- and cadinane-type sesquiterpenoids from the South China Sea sponge Acanthella cavernosa

• Shou-Mao Shen,
• Qing Yang,
• Yi Zang,
• Jia Li,
• Xueting Liu and
• Yue-Wei Guo

Beilstein J. Org. Chem. 2022, 18, 916–925, doi:10.3762/bjoc.18.91

• ) also restricted the application of computational methods. Therefore, the absolute configuration for (+)-4/(−)-4 and (+)-5/(−)-5 remain undefined. As mentioned in a review by William’s group [22], the enantiomeric natural products can arise from a single species or different genera and/or species

• Centre with CCDC number 2173439 (2). The data could be obtained free of charge via http://www.ccdc.cam.ac.uk/data_request/cif. Details of the crystallographic data were shown in Supporting Information File 1. Computational section. TDDFT-ECD calculations. Conformational searches were conducted using the

First series of N-alkylamino peptoid homooligomers: solution phase synthesis and conformational investigation

• Maxime Pypec,
• Laurent Jouffret,
• Claude Taillefumier and
• Olivier Roy

Beilstein J. Org. Chem. 2022, 18, 845–854, doi:10.3762/bjoc.18.85

• studied in detail. Computational studies For the theoretical calculations, acetyl N-(methylamino)dimethylamide model peptoids (Ac-N(NMe)n-NMe2) were used instead of the corresponding synthesized benzyl esters. The model structures were generated using the coordinates extracted from the single crystal X

Thiophene/selenophene-based S-shaped double helicenes: regioselective synthesis and structures

• Mengjie Wang,
• Lanping Dang,
• Wan Xu,
• Zhiying Ma,
• Liuliu Shao,
• Guangxia Wang,
• Chunli Li and
• Hua Wang

Beilstein J. Org. Chem. 2022, 18, 809–817, doi:10.3762/bjoc.18.81

• omitted for clarity. UV–vis absorption spectra of DH-1–3 in CH2Cl2 ([c] = 1 × 10−5 M). Synthetic route to S-shaped double helicenes DH-1–3. Crystal parameters of helicenes DH-1 and DH-2. Supporting Information Supporting Information File 193: Spectral and computational data. Supporting Information File

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

• ). Based on these observations, we concluded that electronic properties of the substituent at the C3 position of a cyclopropene ring have a major impact on the reactivity. A more detailed discussion of this issue is presented in the section devoted to the DFT (density functional theory) computational study

• ourselves exclusively to carrying out laboratory experiments. We turned to DFT calculations (M11 density functional theory) [42][43][44][45][46] to interpret the experimental results. At the beginning of the computational study, we evaluated the relative stability of prototropic tautomers which are formed

Structural basis for endoperoxide-forming oxygenases

• Takahiro Mori and
• Ikuro Abe

Beilstein J. Org. Chem. 2022, 18, 707–721, doi:10.3762/bjoc.18.71

• -configuration. These biochemical and biophysical analyses of NvfI suggested that NvfI catalyzes the endoperoxide formation reaction through a different mechanism from those of COX and FtmOx1. Further computational studies and mechanistical studies are now in progress in our laboratories to clarify the molecular

Syntheses of novel pyridine-based low-molecular-weight luminogens possessing aggregation-induced emission enhancement (AIEE) properties

• Masayori Hagimori,
• Tatsusada Yoshida,
• Yasuhisa Nishimura,
• Yukiko Ogawa and
• Keitaro Tanaka

Beilstein J. Org. Chem. 2022, 18, 580–587, doi:10.3762/bjoc.18.60

• aminopyridines based on the acceptor–donor–acceptor (A–D–A) system exhibit AIEE properties in aqueous media, which may be novel candidate molecules for AIEE. Herein, we report the synthesis, photophysical properties, and computational studies of pyrido[1,2-a]pyrrolo[3,4-d]pyrimidines and N-methyl-4-((pyridin-2

Terpenoids from Glechoma hederacea var. longituba and their biological activities

• Dong Hyun Kim,
• Song Lim Ham,
• Zahra Khan,
• Sun Yeou Kim,
• Sang Un Choi,
• Chung Sub Kim and
• Kang Ro Lee

Beilstein J. Org. Chem. 2022, 18, 555–566, doi:10.3762/bjoc.18.58

• , and cell viability assays. The biological activity assays were performed for all compounds isolated using methods described in Supporting Information File 1. Computational analysis. All conformers of 1–3 used in this study were found using the Macromodel (version 2019-2, Schrödinger LLC) module with

Menadione: a platform and a target to valuable compounds synthesis

• Acácio S. de Souza,
• Ruan Carlos B. Ribeiro,
• Dora C. S. Costa,
• Fernanda P. Pauli,
• David R. Pinho,
• Matheus G. de Moraes,
• Fernando de C. da Silva,
• Luana da S. M. Forezi and
• Vitor F. Ferreira

Beilstein J. Org. Chem. 2022, 18, 381–419, doi:10.3762/bjoc.18.43

• reaction mechanisms: free radical autoxidation, cation radical autoxidation, and thermal intersystem crossing (ISC), using 18O2 labeling, spin-trapping, spectroscopic, mass spectrometric, kinetic, and computational techniques. After several experiments, the obtained results have demonstrated that the 2

Regioselectivity of the S_EAr-based cyclizations and S_EAr-terminated annulations of 3,5-unsubstituted, 4-substituted indoles

• Jonali Das and
• Sajal Kumar Das

Beilstein J. Org. Chem. 2022, 18, 293–302, doi:10.3762/bjoc.18.33

• regioselectivity in favor of the 4,5-fused indole system. Based on their experimental and computational investigations, the researchers hypothesized that Thorpe–Ingold effect could induce dispersive interactions between the indole and styrene moieties, triggering the preferential formation of the 3,4-fused indoles

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

• hydride, and C–C bond-forming reductive elimination. Computational results indicate the origin of regioselectivity is involved in the reductive elimination step. Keywords: C–H activation; density functional theory; hydroacylation; iridium catalysis; regioselectivity; Introduction Organic synthesis is

• 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

The enzyme mechanism of patchoulol synthase

• Houchao Xu,
• Bernd Goldfuss,
• Gregor Schnakenburg and
• Jeroen S. Dickschat

Beilstein J. Org. Chem. 2022, 18, 13–24, doi:10.3762/bjoc.18.2

• results from these experiments are contradictory. The present work reports on a reinvestigation of patchoulol biosynthesis by isotopic labelling experiments and computational chemistry. The results are in favour of a pathway through the neutral intermediates germacrene A and α-bulnesene that are both

• intermolecular deuterium transfers as suggested in these studies were obtained. The results from labelling experiments are furthermore fully supported by DFT calculations. Our computational work also demonstrated that the mechanisms by Croteau et al. [9] and Faraldos et al. [14] are difficult to understand

DABCO-promoted photocatalytic C–H functionalization of aldehydes

• Bruno Maia da Silva Santos,
• Mariana dos Santos Dupim,
• Cauê Paula de Souza,
• Thiago Messias Cardozo and
• Fernanda Gadini Finelli

Beilstein J. Org. Chem. 2021, 17, 2959–2967, doi:10.3762/bjoc.17.205

• strategy for aldehyde C–H activation. The acyl radicals generated in this step were arylated with aryl bromides through a well stablished nickel cross-coupling methodology, leading to a variety of interesting aryl ketones in good yields. We also performed computational calculations to shine light in the

• through this step were used in a well-stablished nickel-catalyzed cross-coupling reaction [19][27][28][29][30] with aryl bromides as a proof of concept, leading to the synthesis of aryl ketones. We also present computational calculations of the HAT reaction step with the DABCO radical cation as the

• computational details. Funding The authors acknowledge the financial support of CAPES.

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

• spectra, supplementary photophysical measurements, computational data obtained from DFT and TD-DFT and electroluminescence data. Supporting Information File 276: xyz Coordinates corresponding to the ground state optimized geometry of DICzTRZ. Funding We thank EU Horizon 2020 Grant Agreement No. 812872

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

• activity (μg/mL). Antifungal activity (μg/mL). Supporting Information Supporting Information File 296: General procedure for the synthesis of ligands (L1–L3) and complexes, NMR spectra and computational data. Funding This work is a part of Samet POYRAZ's ongoing Ph.D. thesis granted by Mersin University

Recent advances in the asymmetric phosphoric acid-catalyzed synthesis of axially chiral compounds

• Alemayehu Gashaw Woldegiorgis and
• Xufeng Lin

Beilstein J. Org. Chem. 2021, 17, 2729–2764, doi:10.3762/bjoc.17.185

• asymmetric bromination reaction afforded monobrominated biaryls with excellent enantioselectivities up to 99% ee (Scheme 4). The experimental and computational studies showed that the highly organized hydrogen-bonding network between a substrate, a chiral phosphoric acid catalyst (CPA 3), and a brominating

GlycoBioinformatics

• Kiyoko F. Aoki-Kinoshita,
• Frédérique Lisacek,
• Niclas Karlsson,
• Daniel Kolarich and
• Nicolle H. Packer

Beilstein J. Org. Chem. 2021, 17, 2726–2728, doi:10.3762/bjoc.17.184

• al. [7], wherein glycan substrate specificities and glycoenzyme reaction rules are described using an improved linear code that is standardized for use in analytical computational tools. This links with McDonald and Davey’s paper [8], which expands on their previously described theoretically derived

N-Sulfinylpyrrolidine-containing ureas and thioureas as bifunctional organocatalysts

• Viera Poláčková,
• Dominika Krištofíková,
• Boglárka Némethová,
• Renata Górová,
• Mária Mečiarová and
• Radovan Šebesta

Beilstein J. Org. Chem. 2021, 17, 2629–2641, doi:10.3762/bjoc.17.176

• reaction conditions for solvent-free Michael additions.a Michael addition of aldehyde 6a–c to nitroalkenes 7a and 7b.a Supporting Information Supporting information contains characterization data for Michael adducts, pictures of NMR spectra, pictures of HPLC chromatograms, and DFT computational details

• . Supporting Information File 310: Characterization data, copies of spectra, and DFT computational details Funding This work was supported by the Slovak Research and Development Agency under the Contract no. APVV-18-0242, and by the Slovak Grant Agency VEGA, grant no. VEGA 1/0332/19. This project has received