A permutation approach to the assignment of the configuration to diastereomeric tetrads by comparison of experimental and ab initio calculated differences in NMR data

• Przemysław J. Boratyński

Beilstein J. Org. Chem. 2017, 13, 2478–2485, doi:10.3762/bjoc.13.245

• from DFT calculation. Then, chemical shift listings are arranged into 24 different arrays corresponding to all permutations. For example data of experimental compounds a, b, c, and d are arranged to computed data for RR, RS, SR, and SS isomers in permutation 1, respectively, RS, RR, SR, and SS in

• are more likely to be accurately modeled by DFT calculation. Reinforcing computational methods by extending the basis set to 6-311G++(2d,2p) for both optimization and NMR calculation steps, as well as applying the MPW1PW91 functional (compounds 1–3) did not affect the comparison significantly. However

• the algorithm a permutation with a highest rank is identified. The major limitation is how accurately the experiment is predicted by the DFT calculation. This is, however, a central problem and any data processing will fail in cases where the computed data do not agree with the experiment

Synthesis and photophysical properties of novel benzophospholo[3,2-b]indole derivatives

• Mio Matsumura,
• Mizuki Yamada,
• Atsuya Muranaka,
• Misae Kanai,
• Naoki Kakusawa,
• Daisuke Hashizume,
• Masanobu Uchiyama and
• Shuji Yasuike

Beilstein J. Org. Chem. 2017, 13, 2304–2309, doi:10.3762/bjoc.13.226

• tetracyclic moieties are planar. The benzophosphole-fused indoles, such as phosphine oxide, phospholium salt, and borane complex, exhibited strong photoluminescence in dichloromethane (Φ = 67–75%). Keywords: benzophospholo[3,2-b]indole; DFT calculation; molecular structure; phosphole derivatives

Self-optimisation and model-based design of experiments for developing a C–H activation flow process

• Alexander Echtermeyer,
• Yehia Amar,
• Jacek Zakrzewski and
• Alexei Lapkin

Beilstein J. Org. Chem. 2017, 13, 150–163, doi:10.3762/bjoc.13.18

• difference between initial guess and final value is significant, which might be caused be the simplifications employed for computing the guesses and the uncertainty of the DFT calculation in the exponentially amplified van’t Hoff equation. The 95% confidence intervals for the parameters of reaction j = 0 are

Protonated paramagnetic redox forms of di-o-quinone bridged with p-phenylene-extended TTF: A EPR spectroscopy study

• Nikolay O. Chalkov,
• Vladimir K. Cherkasov,
• Gleb A. Abakumov,
• Andrey G. Starikov and
• Viacheslav A. Kuropatov

Beilstein J. Org. Chem. 2016, 12, 2450–2456, doi:10.3762/bjoc.12.238

• paramagnetic redox forms of quinone 1 display a rather large spin density on the central p-phenylene fragment. Such delocalization is accessible if the dihedral angle between the p-phenylene and o-semiquinone rings is close to zero. This is in a good agreement with the DFT calculation data at the UB3LYP/6-311

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

• consistent with the increment in the oscillator strength revealed by the DFT calculation results. The ICT absorption peaks are slightly red-shifted and broadened in the solid thin films as compared to those in the chloroform solutions, which can be ascribed to molecular aggregation in the condensed solid

Molecular weight control in organochromium olefin polymerization catalysis by hemilabile ligand–metal interactions

• Stefan Mark,
• Hubert Wadepohl and
• Markus Enders

Beilstein J. Org. Chem. 2016, 12, 1372–1379, doi:10.3762/bjoc.12.131

• -ray diffraction data could be obtained from the active form of chromium polymerization catalysts [61][62][63]. However, DFT calculation is well suitable for studying such interactions. By such methods it is not only possible to estimate the binding energy but also to compare it with that of ethylene

Reactions of N,3-diarylpropiolamides with arenes under superelectrophilic activation: synthesis of 4,4-diaryl-3,4-dihydroquinolin-2(1H)-ones and their derivatives

• Larisa Yu. Gurskaya,
• Diana S. Belyanskaya,
• Dmitry S. Ryabukhin,
• Denis I. Nilov,
• Irina A. Boyarskaya and
• Aleksander V. Vasilyev

Beilstein J. Org. Chem. 2016, 12, 950–956, doi:10.3762/bjoc.12.93

• such a superelectrophilic activation of a N-formyl group, and this reaction did not take place for N-acyl derivatives 6. Additionally a DFT calculation of dications C1 and D1 derived from 5a and 6a, respectively, was carried out to estimate the electrophilic properties of these species. Charge

Catalytic asymmetric formal synthesis of beraprost

• Yusuke Kobayashi,
• Ryuta Kuramoto and
• Yoshiji Takemoto

Beilstein J. Org. Chem. 2015, 11, 2654–2660, doi:10.3762/bjoc.11.285

• expected, both the chemical yield and enantioselectivity were improved, and the adduct 5 was obtained in 92% yield with 80% ee. In our preliminary DFT calculation, the HB-donor moiety would recognize an oxyanion generated from phenolic OH of substrates with tertiary amine moiety of the catalyst. It was

Recent advances in copper-catalyzed C–H bond amidation

• Jie-Ping Wan and
• Yanfeng Jing

Beilstein J. Org. Chem. 2015, 11, 2209–2222, doi:10.3762/bjoc.11.240

• )/Cu(I) process, Himo and co-workers [57] provided a different Cu(II)/Cu(I) mechanism to explain the selectivity of this C-2 amidation transformation based on the study with DFT calculation. As outlined in Scheme 12, the calculation results suggested that the C-2 amidation of indole was possibly

Chiroptical properties of 1,3-diphenylallene-anchored tetrathiafulvalene and its polymer synthesis

• Masashi Hasegawa,
• Junta Endo,
• Seiya Iwata,
• Toshiaki Shimasaki and
• Yasuhiro Mazaki

Beilstein J. Org. Chem. 2015, 11, 972–979, doi:10.3762/bjoc.11.109

• of 3. Synthesis of chiral (R)-PTDPA and (S)-PTDPA. Redox potentials of 3 and PTDPA.a Absorption maxima of 3, 10 and PTDPA.a Supporting Information Supporting Information File 216: Experimental procedures, characterization data, copies of 1H and 13C NMR charts, recyclable chiral HPLC chart and DFT

• calculation summary. Acknowledgements The authors gratefully acknowledge partial financial aid from Kitasato University Research Grant for young researchers. We also thank to Prof. Dr. Takahiro Tsuchiya for helpful discussion. The calculations were performed at the Research Centre for Computational Science

Carboxylated dithiafulvenes and tetrathiafulvalene vinylogues: synthesis, electronic properties, and complexation with zinc ions

• Yunfei Wang and
• Yuming Zhao

Beilstein J. Org. Chem. 2015, 11, 957–965, doi:10.3762/bjoc.11.107

• , thermal gravimetric analysis (TGA) data of 8, and time-dependent (TD) DFT calculation results for compounds 6 and 7. Acknowledgements We thank the Natural Sciences and Engineering Research Council (NSERC) of Canada, Canada Foundation for Innovation (CFI), and Memorial University for financial support.

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

Chemistry of polyhalogenated nitrobutadienes, 14: Efficient synthesis of functionalized (Z)-2-allylidenethiazolidin-4-ones

• Viktor A. Zapol’skii,
• Jan C. Namyslo,
• Mimoza Gjikaj and
• Dieter E. Kaufmann

Beilstein J. Org. Chem. 2014, 10, 1638–1644, doi:10.3762/bjoc.10.170

• -substituted anilines 16–18 two atropisomers were generated. This phenomenon is due to a less hindered rotation of the C–N bond of the former anilines (Figure 1). The steric hindrance is additionally forcing by the s-cis conformation of the nitrobutadiene moiety (cf. Figure 2). A DFT calculation of the energy

Rapid pseudo five-component synthesis of intensively blue luminescent 2,5-di(hetero)arylfurans via a Sonogashira–Glaser cyclization sequence

• Fabian Klukas,
• Alexander Grunwald,
• Franziska Menschel and
• Thomas J. J. Müller

Beilstein J. Org. Chem. 2014, 10, 672–679, doi:10.3762/bjoc.10.60

• ]. The absorption maximum of 2h is considerably shifted bathochromically in comparison to those of 2c, 2e, and 2f. The DFT calculation on structure 2h reveals a twisted ground state structure. In the whole series compound 2j shows the most redshifted absorption maximum and the highest fluorescence

One-pot three-component synthesis and photophysical characteristics of novel triene merocyanines

• Christian Muschelknautz,
• Robin Visse,
• Jan Nordmann and
• Thomas J. J. Müller

Beilstein J. Org. Chem. 2014, 10, 599–612, doi:10.3762/bjoc.10.51

• frequency analysis. The optimized structure of 10a was submitted to a TD-DFT calculation for assigning the experimentally determined absorption characteristics (Table 5). Therefore, the hybrid exchange–correlation functional CAM-B3LYP [58] was implemented and a non-equilibrium solvation [59][60][61][62][63

Synthesis of axially chiral gold complexes and their applications in asymmetric catalyses

• Yin-wei Sun,
• Qin Xu and
• Min Shi

Beilstein J. Org. Chem. 2013, 9, 2224–2232, doi:10.3762/bjoc.9.261

• by DFT calculation reported by Slaughter’s group. The synthesis of P–Au complexes. Asymmetric intramolecular hydroamination catalyzed by Au complexes. Supporting Information Supporting Information File 473: Experimental procedures and characterization date of compounds. Supporting Information File

Olefin metathesis in nano-sized systems

• Didier Astruc,
• Abdou K. Diallo,
• Sylvain Gatard,
• Liyuan Liang,
• Cátia Ornelas,
• Victor Martinez,
• Denise Méry and
• Jaime Ruiz

Beilstein J. Org. Chem. 2011, 7, 94–103, doi:10.3762/bjoc.7.13

• facilitated in dendrimers as compared to the monomer for entropic reasons. Indeed, DFT calculation showed that the catalytic process must involve decoordination of a phosphorus atom, since the interaction of the olefin with the diphosphine complex is non-bonding. The dendritic ruthenium-benzylidene dendrimers

Anthracene appended pyridinium amide–urea conjugate in selective fluorometric sensing of L-N-acetylvaline salt

• Kumaresh Ghosh,
• Tanmay Sarkar and
• Asoke P. Chattopadhyay

Beilstein J. Org. Chem. 2010, 6, 1211–1218, doi:10.3762/bjoc.6.139

• band at higher wavelength and this characteristic change distinguishes it from other anionic substrates studied. The binding interaction has been studied by 1H NMR, fluorescence and UV titration experiments. Keywords: N-acetyl-L-valine salt; DFT calculation; emission decay; fluorometric detection

Self-association of an indole based guanidinium-carboxylate-zwitterion: formation of stable dimers in solution and the solid state

• Carolin Rether,
• Wilhelm Sicking,
• Roland Boese and
• Carsten Schmuck

Beilstein J. Org. Chem. 2010, 6, No. 3, doi:10.3762/bjoc.6.3

• aromatic N...O (2.703 Å), the guanidinium N...O (2.942 Å) and the indole N...O (2.935 Å) are quite short, as mentioned above. The torsion angle between the aromatic scaffold and the guanidinium group is 48.75°. The DFT calculation give an average dihedral angle of 53.57° and lead to the following averaged

Generation of pyridyl coordinated organosilicon cation pool by oxidative Si-Si bond dissociation

• Toshiki Nokami,
• Ryoji Soma,
• Yoshimasa Yamamoto,
• Toshiyuki Kamei,
• Kenichiro Itami and
• Jun-ichi Yoshida

Beilstein J. Org. Chem. 2007, 3, No. 7, doi:10.1186/1860-5397-3-7

• disilanes determined by rotating disk electrode voltammetry (RDE) in Bu4NClO4/CH3CN. Optimized structures of radical cations of 1,2-diphenyldisilane and 1,2-bis [o-(2-pyridyl)- phenyl]disilane obtained by DFT calculation (B3LYP/LANL2DZ). CSI-MS of organosilicon cation 3d at 0°C. Optimized structures of

• cation 3d. Reaction of organosilicon cation 3d with p-tolylmagnesium bromide. Supporting Information Supporting Information File 84: Supporting information. Experimental procedures, spectrum data of new compounds, details of DFT calculation, and 1H/13C NMR spectra. Acknowledgements This work was