Star-shaped and linear π-conjugated oligomers consisting of a tetrathienoanthracene core and multiple diketopyrrolopyrrole arms for organic solar cells

• Hideaki Komiyama,
• Chihaya Adachi and
• Takuma Yasuda

Beilstein J. Org. Chem. 2016, 12, 1459–1466, doi:10.3762/bjoc.12.142

• , rendering the molecules with narrower bandgaps, and broad and strong light absorptions. To gain insight into the geometric and electronic structures of TTA-DPP4 and TTA-DPP2, density functional theory (DFT) calculations were performed at the B3LYP/6-31G(d,p) level. The calculated energy levels and the

Ring-whizzing in polyene-PtL₂ complexes revisited

• Oluwakemi A. Oloba-Whenu,
• Thomas A. Albright and
• Chirine Soubra-Ghaoui

Beilstein J. Org. Chem. 2016, 12, 1410–1420, doi:10.3762/bjoc.12.135

• ; density functional theory (DFT); hapototropic rearrangements; HOMO–LUMO interactions; polyene-ML2 complexes; ring-whizzing; Introduction Polyene–transition metal complexes were found to undergo fluxional rearrangements as early as 1956 with the preparation of Cp2Fe(CO)2 [1]. The migration of an MLn unit

On the mechanism of imine elimination from Fischer tungsten carbene complexes

• Philipp Veit,
• Christoph Förster and
• Katja Heinze

Beilstein J. Org. Chem. 2016, 12, 1322–1333, doi:10.3762/bjoc.12.125

• reaction pathways for the formation of imine E-3 have been considered. For each pathway, density functional theory (DFT) calculations on the B3LYP/LANL2DZ (IEF-PCM toluene) level of theory have been performed to localize minimum structures and energies of the intermediates which are connected by transition

Three new trixane glycosides obtained from the leaves of Jungia sellowii Less. using centrifugal partition chromatography

• Luíse Azevedo,
• Larissa Faqueti,
• Marina Kritsanida,
• Antonia Efstathiou,
• Despina Smirlis,
• Gilberto C. Franchi Jr,
• Grégory Genta-Jouve,
• Sylvie Michel,
• Louis P. Sandjo,
• Raphaël Grougnet and
• Maique W. Biavatti

Beilstein J. Org. Chem. 2016, 12, 674–683, doi:10.3762/bjoc.12.68

• using density functional theory (DFT) at the B3LYP/6-311+g (d,p) level of theory. A check for imaginary frequencies was performed in order to confirm the presence of a real minimum. Calculations of the rotational strengths and excitation energies were realized using time dependent (TD) DFT at the same

Dynamic behavior of rearranging carbocations – implications for terpene biosynthesis

• Stephanie R. Hare and
• Dean J. Tantillo

Beilstein J. Org. Chem. 2016, 12, 377–390, doi:10.3762/bjoc.12.41

• capable of ab initio or density functional theory (DFT) calculations is used to calculate either (1) force constants (via frequency calculation) along the trajectory, either at every point or in periodic increments, or (2) the gradient of the potential energy, depending on the specific integrator chosen

• trajectories initiated from minima and transition states have both been carried out on carbocations [25] and examples of each are described below. While many different quantum chemical methods can be used to carry out trajectory calculations, standard density functional theory (DFT) approaches are most

Versatile deprotonated NHC: C,N-bridged dinuclear iridium and rhodium complexes

• Albert Poater

Beilstein J. Org. Chem. 2016, 12, 117–124, doi:10.3762/bjoc.12.13

• Albert Poater Institut de Química Computacional i Catàlisi, Departament de Química, Universitat de Girona, Campus de Montilivi, E-17071 Girona, Spain 10.3762/bjoc.12.13 Abstract Bearing the versatility of N-heterocyclic carbene (NHC) ligands, here density functional theory (DFT) calculations

Synthesis and reactivity of aliphatic sulfur pentafluorides from substituted (pentafluorosulfanyl)benzenes

• Norbert Vida,
• Jiří Václavík and
• Petr Beier

Beilstein J. Org. Chem. 2016, 12, 110–116, doi:10.3762/bjoc.12.12

• temperature with exclusive regiochemistry on the less substituted double bond of 12 and complete endo stereochemistry (Scheme 5). Employing density functional theory (DFT) with the B3LYP functional [23] and the aug-cc-pVDZ basis set [24][25], we calculated the reaction coordinates leading to four possible

Hydroquinone–pyrrole dyads with varied linkers

• Hao Huang,
• Christoffer Karlsson,
• Maria Strømme,
• Martin Sjödin and
• Adolf Gogoll

Beilstein J. Org. Chem. 2016, 12, 89–96, doi:10.3762/bjoc.12.10

• properties of the monomers were investigated by NMR and UV–vis spectroscopy as well as density functional theory (DFT) calculations. Results and Discussion Synthesis Methyl linker: Synthesis of 3-(2,5-dimethoxybenzyl)-1H-pyrrole (3a) For our target compound 3-(2,5-dimethoxybenzyl)-1H-pyrrole (3a), we

Solving the puzzling competition of the thermal C²–C⁶ vs Myers–Saito cyclization of enyne-carbodiimides

• Anup Rana,
• Mehmet Emin Cinar,
• Debabrata Samanta and
• Michael Schmittel

Beilstein J. Org. Chem. 2016, 12, 43–49, doi:10.3762/bjoc.12.6

• costly multi-reference techniques. An alternative is to apply the unrestricted broken symmetry (U–BS) density functional theory (DFT) approach, which is often in use for larger systems due to its good results [36][37][38][39][40][41][42][43][44][45][46][47][48][49]. Hence, we applied the U–BS DFT

2-Hetaryl-1,3-tropolones based on five-membered nitrogen heterocycles: synthesis, structure and properties

• Yury A. Sayapin,
• Inna O. Tupaeva,
• Alexandra A. Kolodina,
• Eugeny A. Gusakov,
• Vitaly N. Komissarov,
• Igor V. Dorogan,
• Nadezhda I. Makarova,
• Anatoly V. Metelitsa,
• Valery V. Tkachev,
• Sergey M. Aldoshin and
• Vladimir I. Minkin

Beilstein J. Org. Chem. 2015, 11, 2179–2188, doi:10.3762/bjoc.11.236

• intramolecular N–H···O hydrogen bond. The mechanism of the formation of 1,3-tropolones in the reaction of methylene-active five-membered heterocycles with o-chloranil in acetic acid solution has been studied using density functional theory (DFT) methods. The reaction of 2-(2-benzoxa(thia)zolyl)-5,6,7-trichloro

• -1,3-tropolones and 4,5,6,7-tetrachloro-1,3-tropolones in the reaction of methylene-active five-membered heterocycles with o-chloranil using density functional theory (DFT) quantum chemical methods. Molecular and crystal structures of three representative 2-hetaryl-1,3-tropolones have been determined

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

• Gaussian 09 package [70], and molecular visualization was performed with ChemCraft 1.7 (2013) software [71]. Geometry optimization and natural bond orbital (NBO) analysis was performed for compounds 1 and 3 using density functional theory (DFT) with the long-range corrected ωB97XD functional [72][73] and

Mechanism, kinetics and selectivity of selenocyclization of 5-alkenylhydantoins: an experimental and computational study

• Biljana M. Šmit,
• Radoslav Z. Pavlović,
• Dejan A. Milenković and
• Zoran S. Marković

Beilstein J. Org. Chem. 2015, 11, 1865–1875, doi:10.3762/bjoc.11.200

• selenocyclization of 5-alkenylhydantoins leading to fused bicyclic products [24]. To our best knowledge, no previous theoretical work has reported on this reaction. In this paper, density functional theory (DFT) [25][26][27][28] is utilized to understand the mechanism and selectivity of this key step in the

• the internal nucleophile, the amidic nitrogen, to the seleniranium cation yielding the intermediate imidazolinium cations. Their deprotonation is followed by the formation of the fused bicyclic reaction products. Important intermediates and key transition states are studied by using density functional

• theory (DFT) methods. The pathways of the reaction are investigated in detail. There are two regioselective pathways related to 5-exo and 6-endo products. Theoretical calculations and the monitoring of the cyclization reaction using 1H NMR spectroscopy are in a good agreement with the proposed mechanism

A comprehensive study of olefin metathesis catalyzed by Ru-based catalysts

• Albert Poater and
• Luigi Cavallo

Beilstein J. Org. Chem. 2015, 11, 1767–1780, doi:10.3762/bjoc.11.192

• species is also discussed, with either pyridine or phosphine ligands to dissociate. Keywords: cis; density functional theory (DFT); N-heterocyclic carbene; olefin metathesis; ruthenium; Introduction Organic synthesis is based on reactions that drive the formation of carbon–carbon bonds [1]. Olefin

Deproto-metallation of N-arylated pyrroles and indoles using a mixed lithium–zinc base and regioselectivity-computed CH acidity relationship

• Mohamed Yacine Ameur Messaoud,
• Ghenia Bentabed-Ababsa,
• Madani Hedidi,
• Aïcha Derdour,
• Floris Chevallier,
• Yury S. Halauko,
• Oleg A. Ivashkevich,
• Vadim E. Matulis,
• Laurent Picot,
• Valérie Thiéry,
• Thierry Roisnel,
• Vincent Dorcet and
• Florence Mongin

Beilstein J. Org. Chem. 2015, 11, 1475–1485, doi:10.3762/bjoc.11.160

• ]. Based on these results, we here use CH acidities of the aromatic substrates in THF (calculated using the homodesmic reaction approach within the density functional theory (DFT) framework) to attempt a rationalization of the practical results. Results Synthetic aspects In order to prepare the different

Consequences of the electronic tuning of latent ruthenium-based olefin metathesis catalysts on their reactivity

• Karolina Żukowska,
• Eva Pump,
• Aleksandra E. Pazio,
• Krzysztof Woźniak,
• Luigi Cavallo and
• Christian Slugovc

Beilstein J. Org. Chem. 2015, 11, 1458–1468, doi:10.3762/bjoc.11.158

• 5a or 14 (1.829, 1.845 and 1.842 Å, respectively). DFT calculations Density functional theory (DFT) calculations were performed with the aim to learn more about the compounds under investigation especially in view of their peculiar trans–cis isomerization behavior. Geometry optimizations were

Antioxidant potential of curcumin-related compounds studied by chemiluminescence kinetics, chain-breaking efficiencies, scavenging activity (ORAC) and DFT calculations

• Adriana K. Slavova-Kazakova,
• Silvia E. Angelova,
• Timur L. Veprintsev,
• Petko Denev,
• Davide Fabbri,
• Maria Antonietta Dettori,
• Maria Kratchanova,
• Vladimir V. Naumov,
• Aleksei V. Trofimov,
• Rostislav F. Vasil’ev,
• Giovanna Delogu and
• Vessela D. Kancheva

Beilstein J. Org. Chem. 2015, 11, 1398–1411, doi:10.3762/bjoc.11.151

• 4 – density functional theory (DFT) calculations at UB3LYP/6-31+G(d,p) level, applied to explain the structure–activity relationship. Dimers showed 2–2.5-fold higher values of kA than their monomers. Model 2 gives information about the effects of the side chains and revealed much higher antioxidant

Tetrathiafulvalene-based azine ligands for anion and metal cation coordination

• Awatef Ayadi,
• Aziz El Alamy,
• Olivier Alévêque,
• Magali Allain,
• Nabil Zouari,
• Mohammed Bouachrine and
• Abdelkrim El-Ghayoury

Beilstein J. Org. Chem. 2015, 11, 1379–1391, doi:10.3762/bjoc.11.149

• that occurs in ligand L2 leading to a resonance structure that involves the C=N hydrazone bond as it can be seen in (Figure S2, Supporting Information File 1). Theoretical calculations Theoretical calculations based on density functional theory (DFT) methods have been performed with the Gaussian 09

Surprisingly facile CO₂ insertion into cobalt alkoxide bonds: A theoretical investigation

• Willem K. Offermans,
• Claudia Bizzarri,
• Walter Leitner and
• Thomas E. Müller

Beilstein J. Org. Chem. 2015, 11, 1340–1351, doi:10.3762/bjoc.11.144

• density functional theory (DFT) were performed by using the DMol3 program [57][58]. The Perdew–Burke–Ernzerhof functional to account for the exchange correlation of the electrons was applied [59]. A double numerical basis set plus a polarization d-function on all non-hydrogen atoms and a polarization p

Thiazole-induced rigidification in substituted dithieno-tetrathiafulvalene: the effect of planarisation on charge transport properties

• Rupert G. D. Taylor,
• Joseph Cameron,
• Iain A. Wright,
• Neil Thomson,
• Olena Avramchenko,
• Alexander L. Kanibolotsky,
• Anto R. Inigo,
• Tell Tuttle and
• Peter J. Skabara

Beilstein J. Org. Chem. 2015, 11, 1148–1154, doi:10.3762/bjoc.11.129

• and electrochemical properties of compounds 1 and 2 have been measured by UV–vis spectroscopy and cyclic voltammetry and the results compared with density functional theory (DFT) calculations to confirm the observed properties. Organic field effect transistor (OFET) devices fabricated from 1 and 2

New tris- and pentakis-fused donors containing extended tetrathiafulvalenes: New positive electrode materials for rechargeable batteries

• Shintaro Iwamoto,
• Yuu Inatomi,
• Daisuke Ogi,
• Satoshi Shibayama,
• Yukiko Murakami,
• Minami Kato,
• Kazuyuki Takahashi,
• Kazuyoshi Tanaka,
• Nobuhiko Hojo and
• Yohji Misaki

Beilstein J. Org. Chem. 2015, 11, 1136–1147, doi:10.3762/bjoc.11.128

• obtained as stable solids. Theoretical calculations We performed theoretical calculations of 5A, 6Aa and 7Aa by using the Gaussian 09 program based on the density functional theory (DFT) at the B3LYP/6-31G(d) level [27]. Their HOMO and HOMO–n (n = 1–2 and 1–4) of the trans isomers of 5a, 6a and 8a are

Single-molecule conductance of a chemically modified, π-extended tetrathiafulvalene and its charge-transfer complex with F₄TCNQ

• Raúl García,
• M. Ángeles Herranz,
• Edmund Leary,
• M. Teresa González,
• Gabino Rubio Bollinger,
• Marius Bürkle,
• Linda A. Zotti,
• Yoshihiro Asai,
• Fabian Pauly,
• Juan Carlos Cuevas,
• Nicolás Agraït and
• Nazario Martín

Beilstein J. Org. Chem. 2015, 11, 1068–1078, doi:10.3762/bjoc.11.120

• experimental resolution, based on the value we measure for the CT complex. Ab initio calculations To gain insight into the conduction mechanism of compound 5, we performed theoretical calculations based on a combination of density functional theory (DFT) and Green’s functions techniques within the framework of

First principle investigation of the linker length effects on the thermodynamics of divalent pseudorotaxanes

• Andreas J. Achazi,
• Doreen Mollenhauer and
• Beate Paulus

Beilstein J. Org. Chem. 2015, 11, 687–692, doi:10.3762/bjoc.11.78

• linker shows an enhanced binding strength due to electronic effects, namely the dispersion interaction between the linkers from the guest and the host. For the longer linkers this ideal packing is not possible due to steric hindrance. Keywords: density functional theory (DFT); dispersion correction

On the strong difference in reactivity of acyclic and cyclic diazodiketones with thioketones: experimental results and quantum-chemical interpretation

• Andrey S. Mereshchenko,
• Alexey V. Ivanov,
• Viktor I. Baranovskii,
• Grzegorz Mloston,
• Ludmila L. Rodina and
• Valerij A. Nikolaev

Beilstein J. Org. Chem. 2015, 11, 504–513, doi:10.3762/bjoc.11.57

• -thioxocyclobutanone (2b) as dipolarophiles (Figure 1). The calculations were performed at the density functional theory (DFT) level using the 6-31G(d) basis set. For reactions of diazo compounds 1a–f with thiobenzophenone (2a), the solvent was simulated using the polarizable continuum model (PCM) [22], and for the

Synthesis of dinucleoside acylphosphonites by phosphonodiamidite chemistry and investigation of phosphorus epimerization

• William H. Hersh

Beilstein J. Org. Chem. 2015, 11, 184–191, doi:10.3762/bjoc.11.19

• acylphosphonites, (3) conversion of these compounds to phosphorothioates, (4) evidence that acylphosphonites, unlike their phosphine analogs, do not undergo facile inversion, and (5) confirmation of this observation by density functional theory (DFT) calculations. Results and Discussion Synthesis of

Binding mode and free energy prediction of fisetin/β-cyclodextrin inclusion complexes

• Bodee Nutho,
• Wasinee Khuntawee,
• Chompoonut Rungnim,
• Piamsook Pongsawasdi,
• Peter Wolschann,
• Alfred Karpfen,
• Nawee Kungwan and
• Thanyada Rungrotmongkol

Beilstein J. Org. Chem. 2014, 10, 2789–2799, doi:10.3762/bjoc.10.296

• binding free energies were also corrected with quantum mechanics energy (∆EQM) by replacing the MM energy (∆EMM) in Equation 3 with density functional theory (DFT) calculation using the M06-2X functional with 6-31G(d,p) level of basis set. Besides, the full optimization in gas phase and PCM water model of