A review of the total syntheses of triptolide

• Xiang Zhang,
• Zaozao Xiao and
• Hongtao Xu

Beilstein J. Org. Chem. 2019, 15, 1984–1995, doi:10.3762/bjoc.15.194

• -endo-trig cyclization of 2-alkenyl-1,3-dithiolanes to access trans-decalins (Figure 2, route K) [78]. Density functional theory calculation (DFT) studies indicated that the 2-alkenyl-1,3-dithiolane moiety acts as a latent initiator, which triggers the cationic 6-endo-trig cyclization in the presence of

Functional panchromatic BODIPY dyes with near-infrared absorption: design, synthesis, characterization and use in dye-sensitized solar cells

• Quentin Huaulmé,
• Cyril Aumaitre,
• Outi Vilhelmiina Kontkanen,
• David Beljonne,
• Alexandra Sutter,
• Gilles Ulrich,
• Renaud Demadrille and
• Nicolas Leclerc

Beilstein J. Org. Chem. 2019, 15, 1758–1768, doi:10.3762/bjoc.15.169

• were computed by density functional theory modelling (DFT) and characterized through UV–vis spectroscopy and cyclic voltammetry (CV) measurements. Finally, we report preliminary results obtained using these functional dyes as photosensitizers in dye-sensitized solar cells (DSSCs). Keywords: boron

• BODIPY derivative, we decided to synthetize the two molecular structures disclosed in Figure 1, namely BOD-TTPA-alk and BOD-TTPA. To support our molecular design, and especially to have better insight on the electronic structure and optical properties of the dyes, we performed (time-dependent) density

• functional theory (TD-DFT) calculations on the four representative molecules displayed in Figure 2: Dyes (1 and 3) vs (2 and 4) differ by the position (2,6 or 1,7) of the methyl groups on the BODIPY core, while dyes (1 and 2) vs (3 and 4) differ by the presence (or not) of a triphenylamine donor group on the

Synthesis, photophysical and electrochemical properties of pyridine, pyrazine and triazine-based (D–π–)₂A fluorescent dyes

• Keiichi Imato,
• Toshiaki Enoki,
• Koji Uenaka and
• Yousuke Ooyama

Beilstein J. Org. Chem. 2019, 15, 1712–1721, doi:10.3762/bjoc.15.167

• properties of the three dyes were investigated by photoabsorption and fluorescence spectroscopy, Lippert–Mataga plots, cyclic voltammetry and density functional theory calculations. The photoabsorption maximum (λmax,abs) and the fluorescence maximum (λmax,fl) for the intramolecular charge-transfer

• , Lippert–Mataga plots, cyclic voltammetry and density functional theory (DFT) calculations, we reveal the photophysical and electrochemical properties of the (D–π–)2A fluorescent dyes OUY-2, OUK-2 and OUJ-2. Results and Discussion Synthesis The (D–π–)2A fluorescent dyes OUY-2 [2], OUK-2 [3][4] and OUJ-2

Water inside β-cyclodextrin cavity: amount, stability and mechanism of binding

• Stiliyana Pereva,
• Valya Nikolova,
• Silvia Angelova,
• Tony Spassov and
• Todor Dudev

Beilstein J. Org. Chem. 2019, 15, 1592–1600, doi:10.3762/bjoc.15.163

• experimental) approaches are sometimes conflicting and contradictory. There is no “standard” method to investigate the complexation behavior of CDs. Thus, in our study a computational quantum mechanical modelling method, namely density functional theory (DFT) was chosen to investigate the electronic structure

Synthesis of dipolar molecular rotors as linkers for metal-organic frameworks

• Sebastian Hamer,
• Fynn Röhricht,
• Marius Jakoby,
• Ian A. Howard,
• Xianghui Zhang,
• Christian Näther and
• Rainer Herges

Beilstein J. Org. Chem. 2019, 15, 1331–1338, doi:10.3762/bjoc.15.132

• dicarboxylic acid-substituted dipolar molecular rotors for the use as linker molecules in metal-organic frameworks (MOFs). The rotor molecules exhibit very low rotational barriers and decent to very high permanent, charge free dipole moments, as shown by density functional theory calculations on the isolated

• /def2SVP level of density functional theory. For this evaluation both carboxylic groups where fixed in a plane. In all cases, barriers for rotations are below 2 kcal mol−1. In the absence of intermolecular interactions there should be thermally excited rotation at room temperature and down to very low

Host–guest interactions between p-sulfonatocalix[4]arene and p-sulfonatothiacalix[4]arene and group IA, IIA and f-block metal cations: a DFT/SMD study

• Valya K. Nikolova,
• Cristina V. Kirkova,
• Silvia E. Angelova and
• Todor M. Dudev

Beilstein J. Org. Chem. 2019, 15, 1321–1330, doi:10.3762/bjoc.15.131

• between biological receptors and small ions. The complex formation behavior of water-soluble p-sulfonatocalix[4]arene and thiacalix[4]arene and group IA, IIA and f-block metal cations has been investigated computationally by means of density functional theory computations in the gas phase and in aqueous

• ]. Conclusion A systematic theoretical study of the group IA, IIA and f-block metal ions binding characteristics to p-sulfonatocalix[4]arene (C[4]A) and p-sulfonatothiacalix[4]arene (TC[4]A) has been performed using density functional theory combined with solvation model based on density (SMD) calculations. It

Mechanochemical Friedel–Crafts acylations

• Mateja Đud,
• Anamarija Briš,
• Iva Jušinski,
• Davor Gracin and
• Davor Margetić

Beilstein J. Org. Chem. 2019, 15, 1313–1320, doi:10.3762/bjoc.15.130

• transient reactive intermediates were predicted by density functional theory method B3LYP/6-31G* (Supporting Information File 1) [61]. The stretching of the +C≡O bond of the acylium ion was predicted to be at about 2300 cm−1. Raman spectroscopy revealed that the complexation of phthalic anhydride with AlCl3

Mechanochemical amorphization of chitin: impact of apparatus material on performance and contamination

• Thomas Di Nardo and
• Audrey Moores

Beilstein J. Org. Chem. 2019, 15, 1217–1225, doi:10.3762/bjoc.15.119

• systematic study of the effects of a number of medium parameters onto a model reaction, namely the amorphization of chitin where interchain stabilization is greater than 250 kJ/mol based on density functional theory (DFT) calculation [58]. We explored the role of the material of the jar and the ball, ball

Mechanochemical synthesis of hyper-crosslinked polymers: influences on their pore structure and adsorption behaviour for organic vapors

• Sven Grätz,
• Sebastian Zink,
• Hanna Kraffczyk,
• Marcus Rose and
• Lars Borchardt

Beilstein J. Org. Chem. 2019, 15, 1154–1161, doi:10.3762/bjoc.15.112

• proposed by Rouquerol and Llewellyn. Pore size distributions were calculated using the quenched solid density functional theory (QSDFT) method for carbon (slit pores, equilibrium kernel) on the adsorption branch. Total pore volumes were determined from the adsorption branch at p/p0 = 0.95. Prior to

Precious metal-free molecular machines for solar thermal energy storage

• Meglena I. Kandinska,
• Snejana M. Kitova,
• Vladimira S. Videva,
• Stanimir S. Stoyanov,
• Stanislava B. Yordanova,
• Stanislav B. Baluschev,
• Silvia E. Angelova and
• Aleksey A. Vasilev

Beilstein J. Org. Chem. 2019, 15, 1096–1106, doi:10.3762/bjoc.15.106

• photoisomerization with lifetimes of the higher energy form longer than 500 seconds. Density functional theory (DFT) calculations at the B3LYP/6-31+G(d,p) level were performed in order to predict the enthalpies (H) of the cis and trans isomers and the storage energies (ΔH) for the systems studied. Keywords: aza-15

• density functional theory (DFT) calculations at the B3LYP/6-31+G(d,p) level. The first step in the molecular modelling investigation was the optimization of the molecular structures of the cis and trans isomers of dyes 4a–d (with the –(CH2)nSO3− (n = 3, 4) tails oriented to be in proximity to the aza-15

• polarizable continuum model (PCM) did not provide a good quantitative agreement with the experimental stability constants [23] so the data for ∆∆H in acetonitrile are not provided. Time-dependent density functional theory (TDDFT) calculations were used to probe the electronic reorganizations upon excitation

An anomalous addition of chlorosulfonyl isocyanate to a carbonyl group: the synthesis of ((3aS,7aR,E)-2-ethyl-3-oxo-2,3,3a,4,7,7a-hexahydro-1H-isoindol-1-ylidene)sulfamoyl chloride

• Aytekin Köse,
• Aslı Ünal,
• Ertan Şahin,
• Uğur Bozkaya and
• Yunus Kara

Beilstein J. Org. Chem. 2019, 15, 931–936, doi:10.3762/bjoc.15.89

• release of carbon dioxide from the molecule. We performed theoretical computations to better understand the reaction mechanism shown in Scheme 4 (Figure 3). For this purpose, we employed density functional theory (DFT) calculations and performed geometric optimizations using the B3LYP functional [19][20

Photochemical generation of the 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) radical from caged nitroxides by near-infrared two-photon irradiation and its cytocidal effect on lung cancer cells

• Ayato Yamada,
• Manabu Abe,
• Yoshinobu Nishimura,
• Shoji Ishizaka,
• Masashi Namba,
• Taku Nakashima,
• Kiyofumi Shimoji and
• Noboru Hattori

Beilstein J. Org. Chem. 2019, 15, 863–873, doi:10.3762/bjoc.15.84

• yields in DMSO of 5a and 5b were determined to be 16.1 and 8.6%, respectively, although no emission was observed from these compounds in non-polar benzene, indicating that the excited state has zwitterionic character. The charge transfer transition was supported by time-dependent density functional

Strong hyperconjugative interactions limit solvent and substituent influence on conformational equilibrium: the case of cis-2-halocyclohexylamines

• Camila B. Francisco,
• Cleverton S. Fernandes,
• Ulisses Z. de Melo,
• Roberto Rittner,
• Gisele F. Gauze and
• Ernani A. Basso

Beilstein J. Org. Chem. 2019, 15, 818–829, doi:10.3762/bjoc.15.79

• (Cartesian coordinates are available in Supporting Information File 1). The calculations were performed using the M06-2X density functional method, and the second-order Möller–Plesset perturbation method (MP2), associated with the Pople 6-311++G(2df,2p), and Dunning aug-cc-pVDZ basis set. The mixed basis set

A diastereoselective approach to axially chiral biaryls via electrochemically enabled cyclization cascade

• Hong Yan,
• Zhong-Yi Mao,
• Zhong-Wei Hou,
• Jinshuai Song and
• Hai-Chao Xu

Beilstein J. Org. Chem. 2019, 15, 795–800, doi:10.3762/bjoc.15.76

• moiety leads to the formation of 3a. Based on the proposed reaction mechanism and the results mentioned above, the cyclization of vinyl radical IV to give V is the atroposelective step. Density functional theory (DFT)-based calculations suggested that the cyclization of IV could be explained by a Curtin

Catalyst-free assembly of giant tris(heteroaryl)methanes: synthesis of novel pharmacophoric triads and model sterically crowded tris(heteroaryl/aryl)methyl cation salts

• Rodrigo Abonia,
• Luisa F. Gutiérrez,
• Braulio Insuasty,
• Jairo Quiroga,
• Kenneth K. Laali,
• Chunqing Zhao,
• Gabriela L. Borosky,
• Samantha M. Horwitz and
• Scott D. Bunge

Beilstein J. Org. Chem. 2019, 15, 642–654, doi:10.3762/bjoc.15.60

• over MgSO4, and concentrated under reduced pressure. Finally, the crystals were obtained after simple trituration with Et2O. Computational methods. Density functional theory (DFT) calculations were carried out with the Gaussian 09 program suite [66]. Geometries were fully optimized at the B3LYP [67][68

Computational characterization of enzyme-bound thiamin diphosphate reveals a surprisingly stable tricyclic state: implications for catalysis

• Ferran Planas,
• Michael J. McLeish and
• Fahmi Himo

Beilstein J. Org. Chem. 2019, 15, 145–159, doi:10.3762/bjoc.15.15

• understanding of the kinetics and mechanism of the individual reactions. In this paper we use density functional theory calculations to systematically study the different cofactor states in terms of energies and geometries. Benzoylformate decarboxylase (BFDC), which is a well characterized chiral catalyst

• the enzyme [19][20]. Thirty years later, density functional theory (DFT) calculations showed that the 4′-amino moiety of the cofactor can either accept or donate a proton in the reactions, depending on the protonation state of N1′ [21]. Orbital analysis of the IP/YIH+ reaction showed that full

• substrates or, possibly more importantly, the evolution of ThDP-dependent enzymes to accept a wide range of non-native substrates, might not be as simple as may have been expected. Experimental All calculations were performed with the B3LYP-D3(BJ) [62][63][64][65] density functional method and using the

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

• : “Understanding the physics and chemistry of large molecules and solids would have been practically impossible if not for the principle of transferability” [43]. In the language of density functional theory, the concept of near-sightedness of electrons “…describes the fact that, for fixed chemical potential

Dispersion interactions

• Peter R. Schreiner

Beilstein J. Org. Chem. 2018, 14, 3076–3077, doi:10.3762/bjoc.14.286

• for all matter starting from atoms (e.g., the condensation of helium) over molecules (e.g., aggregation) to materials (e.g., adhesion). It is also difficult to include in theoretical approaches and for the longest time it had been left virtually unnoticed that many density functional theory (DFT

The activity of indenylidene derivatives in olefin metathesis catalysts

• Maria Voccia,
• Steven P. Nolan,
• Luigi Cavallo and
• Albert Poater

Beilstein J. Org. Chem. 2018, 14, 2956–2963, doi:10.3762/bjoc.14.275

• turnover event of an olefin metathesis reaction using a new family of homogenous Ru-based catalysts bearing modified indenylidene ligands has been investigated, using methoxyethylene as a substrate. The study is carried out by means of density functional theory (DFT). The indenylidene ligands are decorated

• [29][30][31]. We are interested in evaluating, by density functional theory (DFT) calculations, the difference in the activation step between complexes 1–6 in Scheme 1, whose reactivity and properties have been reported already (for 1 and 2) [24][32][33]. Predictive catalysis will be used here to

The influence of the cationic carbenes on the initiation kinetics of ruthenium-based metathesis catalysts; a DFT study

• Magdalena Jawiczuk,
• Angelika Janaszkiewicz and
• Bartosz Trzaskowski

Beilstein J. Org. Chem. 2018, 14, 2872–2880, doi:10.3762/bjoc.14.266

• . The excess positive charge of the quaternary ammonium is, in most cases, distributed over the imidazole core and mesityl groups and does not affect the ruthenium core nor the ruthenium–Ccarbene bond. Experimental We used density functional theory (DFT) using a computational protocol similar to our

• optimization step we used the M06 density functional with the 6-31G** basis set for C, N, O, Cl and H atoms, while the Ru atom, which was described by the Los Alamos angular momentum projected effective core potential (ECP) using the double-ζ contraction of valence functions (denoted as LACVP**). The choice of

Unprecedented nucleophile-promoted 1,7-S or Se shift reactions under Pummerer reaction conditions of 4-alkenyl-3-sulfinylmethylpyrroles

• Takashi Go,
• Akane Morimatsu,
• Hiroaki Wasada,
• Genzoh Tanabe,
• Osamu Muraoka,
• Yoshiharu Sawada and
• Mitsuhiro Yoshimatsu

Beilstein J. Org. Chem. 2018, 14, 2722–2729, doi:10.3762/bjoc.14.250

• key intermediate 15, of which the sulfanyl group would intramolecularly migrate to produce 16 stereoselectively (path c, not d). The hydrolysis of 16 using TBAH yields diol 17. We further confirmed the mechanism of the 1,7-S shift reaction by performing density functional theory (DFT)-based

Dispersion-mediated steering of organic adsorbates on a precovered silicon surface

• Lisa Pecher,
• Sebastian Schmidt and
• Ralf Tonner

Beilstein J. Org. Chem. 2018, 14, 2715–2721, doi:10.3762/bjoc.14.249

• the neighbouring adsorption site. This helps in understanding the nonstatistical pattern formation for this surface–adsorbate system and hints toward an inclusion of dispersion attraction as another determining factor for surface adsorption. Keywords: bonding analysis; cyclooctyne; density functional

• adsorption of a molecule on a pre-covered surface using density functional theory (DFT) approaches with and without dispersion correction terms. In contrast to the above-mentioned intermediate-based selectivity, the steering-type interaction takes place before covalent bonds between molecule and surface are

A challenging redox neutral Cp*Co(III)-catalysed alkylation of acetanilides with 3-buten-2-one: synthesis and key insights into the mechanism through DFT calculations

• Andrew Kenny,
• Alba Pisarello,
• Arron Bird,
• Paula G. Chirila,
• Alex Hamilton and
• Christopher J. Whiteoak

Beilstein J. Org. Chem. 2018, 14, 2366–2374, doi:10.3762/bjoc.14.212

• procedure provides a wide substrate scope in terms of substituted acetanilides, although the optimised conditions were found to be more forcing than those for the corresponding benzamide substrates. Interestingly, density functional theory (DFT) studies reveal that the major impediment in the mechanism is

Hydroarylations by cobalt-catalyzed C–H activation

• Rajagopal Santhoshkumar and
• Chien-Hong Cheng

Beilstein J. Org. Chem. 2018, 14, 2266–2288, doi:10.3762/bjoc.14.202

• yields with anti-selectivity. The alkene product originally should be syn-13, but it rearranged to anti-13 at the high reaction temperature likely catalyzed by the cobalt complex. Moreover, the found intermolecular KIE of 1.4 and density functional theory (DFT) calculations strongly suggest that the

Cobalt-catalyzed peri-selective alkoxylation of 1-naphthylamine derivatives

• Jiao-Na Han,
• Cong Du,
• Xinju Zhu,
• Zheng-Long Wang,
• Yue Zhu,
• Zhao-Yang Chu,
• Jun-Long Niu and
• Mao-Ping Song

Beilstein J. Org. Chem. 2018, 14, 2090–2097, doi:10.3762/bjoc.14.183

• previous literature [30][31][46][47], a plausible reaction mechanism for cobalt-catalyzed alkoxylation was proposed. As shown in Scheme 4, initially, CoIIX2 could be oxidized to CoIIIX2OR in the presence of a silver salt and an alcohol. Based on the experiments and the density functional theory