Anodic coupling of carboxylic acids to electron-rich double bonds: A surprising non-Kolbe pathway to lactones

• Robert J. Perkins,
• Hai-Chao Xu,
• John M. Campbell and
• Kevin D. Moeller

Beilstein J. Org. Chem. 2013, 9, 1630–1636, doi:10.3762/bjoc.9.186

• to initial formation of N-localized radical 6. Depending on the reaction conditions, the experiment favoured either a sulfonamide or alcohol based cyclization. Density functional theory (DFT) calculations suggested that sulfonamide based cyclizations proceed by addition of the N-localized radical to

Enhancement of efficiency in organic photovoltaic devices containing self-complementary hydrogen-bonding domains

• Rohan J. Kumar,
• Jegadesan Subbiah and
• Andrew B. Holmes

Beilstein J. Org. Chem. 2013, 9, 1102–1110, doi:10.3762/bjoc.9.122

• significantly compared with the N-alkylated compound. Density functional theory (DFT) calculations, at the B3YLP-61G*(d,p) level of theory using the Gaussian ‘09 suite of programs [28], result in the observation of a polar distribution of the calculated molecular orbital densities for 2, as expected from the

An aniline dication-like transition state in the Bamberger rearrangement

• Shinichi Yamabe,
• Guixiang Zeng,
• Wei Guan and
• Shigeyoshi Sakaki

Beilstein J. Org. Chem. 2013, 9, 1073–1082, doi:10.3762/bjoc.9.119

• rearrangement. Theoretical calculations The reacting systems were investigated by density functional theory (DFT) calculations. The B3LYP [8][9] method was used to trace the reaction path. The basis sets employed were 6-31G(d) and 6-311+G(d,p), where the latter was adopted for the key (OH transfer) steps. For

Synthesis, photophysical and electrochemical characterization of terpyridine-functionalized dendritic oligothiophenes and their Ru(II) complexes

• Amaresh Mishra,
• Elena Mena-Osteritz and
• Peter Bäuerle

Beilstein J. Org. Chem. 2013, 9, 866–876, doi:10.3762/bjoc.9.100

• nonemissive [Ru(tpy)2]2+ center of the metallodendrimer. Quantum chemical calculations. In order to gain insight into the structural properties, the electron density distribution of the frontier orbitals of both complexes was analyzed by density functional theory (DFT) using the B3LYP/LANL2DZ basis set

• platinum wire, and the reference electrode was an Ag/AgCl secondary electrode. All potentials were internally referenced to the ferrocene/ferricenium couple. Calculations. Full geometry optimizations were performed in the gas phase by using density functional theory (DFT) calculations based on the B3LYP

• oligothienylene-ethynylene dendrons and their corresponding terpyridine-based ligands. Their complexation with Ru(II) led to interesting novel metallodendrimers with rich spectroscopic properties. All new compounds were fully characterized by 1H and 13C NMR, as well as MALDI–TOF mass spectra. Density functional

Gold-catalyzed oxycyclization of allenic carbamates: expeditious synthesis of 1,3-oxazin-2-ones

• Benito Alcaide,
• Pedro Almendros,
• M. Teresa Quirós and
• Israel Fernández

Beilstein J. Org. Chem. 2013, 9, 818–826, doi:10.3762/bjoc.9.93

• the gold to the distal allenic double bond leading to complex 9, followed by a 6-exo-dig oxyauration is likely for the achievement of 1,3-oxazin-2-ones 4 from allenic carbamates 2 (Scheme 4, right-hand catalytic cycle). Density functional theory (DFT) calculations (see Supporting Information File 1

Direct alkenylation of indolin-2-ones by 6-aryl-4-methylthio-2H-pyran-2-one-3-carbonitriles: a novel approach

• Sandeep Kumar,
• Ramendra Pratap,
• Abhinav Kumar,
• Brijesh Kumar,
• Vishnu K. Tandon and
• Vishnu Ji Ram

Beilstein J. Org. Chem. 2013, 9, 809–817, doi:10.3762/bjoc.9.92

• interaction. Hence, density functional theory (DFT) calculations also indicate that the tautomer 8y is relatively more stable than 8x and 8z (Figure 2). Further, in order to generalize the reaction, attempts were made for the alkenylation of indolin-2-one with 6-aryl-4-sec-amino-2H-pyran-2-one-3-carbonitriles

• 1.053, largest difference peak and hole 0.455 and −0.644 e·Å−3. Computational details Geometric characterization of all of the three tautomers of 8yc was performed at the level of density functional theory (DFT) using the B3LYP functional [48][49]. For all the atoms 6-31G** basis sets were used. All

Photoionisation of the tropyl radical

• Kathrin H. Fischer,
• Patrick Hemberger,
• Andras Bodi and
• Ingo Fischer

Beilstein J. Org. Chem. 2013, 9, 681–688, doi:10.3762/bjoc.9.77

• chose a (7,7) active space and employed a 6-31G(d) basis set. For the cation the input parameters were calculated by density functional theory (DFT) with the Gaussian 09 suite of programs [35], employing the B3LYP functional and a 6-31G(d) basis set. For a closed-shell molecule without vibronic

Complete σ* intramolecular aromatic hydroxylation mechanism through O₂ activation by a Schiff base macrocyclic dicopper(I) complex

• Albert Poater and
• Miquel Solà

Beilstein J. Org. Chem. 2013, 9, 585–593, doi:10.3762/bjoc.9.63

• was not possible to trap or detect any intermediate in the path from a + O2 → g. Here, by means of density functional theory (DFT) calculations, we search for the whole reaction pathway (Figure 1). The results are compared with those obtained in a similar previous study in which the hexaazamacrocyclic

A new family of four-ring bent-core nematic liquid crystals with highly polar transverse and end groups

• Kalpana Upadhyaya,
• Venkatesh Gude,
• Golam Mohiuddin and
• Rao V. S. Nandiraju

Beilstein J. Org. Chem. 2013, 9, 26–35, doi:10.3762/bjoc.9.4

• to possibly weakened lateral interactions and increased intermolecular spacing between molecules. Density functional theory calculations The quantum mechanical calculations of molecular properties in the gas phase were performed by using density functional theory (DFT) [58] employing the combination

Theoretical study on β-cyclodextrin inclusion complexes with propiconazole and protonated propiconazole

• Adrian Fifere,
• Narcisa Marangoci,
• Stelian Maier,
• Adina Coroaba,
• Dan Maftei and
• Mariana Pinteala

Beilstein J. Org. Chem. 2012, 8, 2191–2201, doi:10.3762/bjoc.8.247

• geometry optimization, due to its improved description of hydrogen bonds and steric effects [8][9][10]. Advanced methods, such as Hartree–Fock (HF) and density functional theory (DFT), were also applied in cyclodextrin chemistry to explain experimental data [11][12]. Very often, ab initio methods are used

Synthesis, solid-state fluorescence properties, and computational analysis of novel 2-aminobenzo[4,5]thieno[3,2-d]pyrimidine 5,5-dioxides

• Kenichirou Yokota,
• Masayori Hagimori,
• Naoko Mizuyama,
• Yasuhisa Nishimura,
• Hiroshi Fujito,
• Yasuhiro Shigemitsu and
• Yoshinori Tominaga

Beilstein J. Org. Chem. 2012, 8, 266–274, doi:10.3762/bjoc.8.28

• % and 65% yield, respectively. Computational methods The ground-state (S0) geometries were optimized by means of density functional theory (DFT) with the B3LYP hybrid functional and 6-311G(d,p) [11] basis set (DFT(B3LYP)/6-311G(d,p)). The first excited-state (S1) geometries were optimized with

The interplay of configuration and conformation in helical perylenequinones: Insights from chirality induction in liquid crystals and calculations

• Elisa Frezza,
• Silvia Pieraccini,
• Stefania Mazzini,
• Alberta Ferrarini and
• Gian Piero Spada

Beilstein J. Org. Chem. 2012, 8, 155–163, doi:10.3762/bjoc.8.16

• give 1 and 2 a limited, though non-negligible conformational freedom. To understand the relation between molecular structure and chiral induction in liquid crystals, we integrated measurements of helical twisting power (HTP) with a conformational analysis, performed by density functional theory (DFT

On the control of secondary carbanion structure utilising ligand effects during directed metallation

• Andrew E. H. Wheatley,
• Jonathan Clayden,
• Ian H. Hillier,
• Alison Campbell Smith,
• Mark A. Vincent,
• Laurence J. Taylor and
• Joanna Haywood

Beilstein J. Org. Chem. 2012, 8, 50–60, doi:10.3762/bjoc.8.5

• signals at δ 7.13–7.00 ppm for 6-H, at δ 6.88 (1H), 6.46 (1H), 6.38 (1H), 5.63 (1H) ppm for the dominant lithiate, and at δ 6.74 (0.15H), 6.63 (0.3H), 5.69 (0.15H) ppm for the minor lithiate. Computational studies The structures of 6-Lil·L (L = PMDTA, DGME) were optimised using density functional theory

• (DFT) calculations. For the use of either Lewis base, two isomeric forms of 6-Lil were modelled. These were the cis and trans isomers expected to arise from slow rotation about the partially double arene–(α-C) bond (see above). For each Lewis base, calculation of the trans isomer identified two minimum

Gold-catalyzed heterocyclizations in alkynyl- and allenyl-β-lactams

• Benito Alcaide and
• Pedro Almendros

Beilstein J. Org. Chem. 2011, 7, 622–630, doi:10.3762/bjoc.7.73

• five-membered oxacycle. A computational study (using density functional theory, DFT) of the above heterocyclization has been carried out [50]. The Au(III)-catalyzed cyclization of γ-allenol I (Figure 1) takes place regio- and stereoselectively through a 5-exo hydroalkoxylation because of a kinetic

• latter, despite that fact that a priori this should be energetically more demanding. Conclusion In summary, regiocontrolled gold-catalyzed heterocyclization reactions of 2-azetidinone-tethered allenes and alkynes which lead to a variety of oxa- and azacycles have been developed. Density functional theory

• (DFT) calculations were performed to obtain insight on various aspects of this reactivity and indicated the selective activation of the allene and alkyne component. Free energy profile [kcal mol–1] for the transformation of γ-allenol I into the tetrahydrofuran type 9. Gold-catalyzed cyclization of 4

A new fluorescent chemosensor for fluoride anion based on a pyrrole–isoxazole derivative

• Zhipei Yang,
• Kai Zhang,
• Fangbin Gong,
• Shayu Li,
• Jun Chen,
• Jin Shi Ma,
• Lyubov N. Sobenina,
• Albina I. Mikhaleva,
• Guoqiang Yang and
• Boris A. Trofimov

Beilstein J. Org. Chem. 2011, 7, 46–52, doi:10.3762/bjoc.7.8

• with DMSO-d6 as solvent and tetramethylsilane (TMS) as internal standard. Theoretical method. Density functional theory (DFT) calculations were carried out by means of the Gaussian suite of programs to optimize the structure parameters of receptor 1 and its anionic forms. Becke’s three-parameter

Intramolecular hydroxycarbene C–H-insertion: The curious case of (o-methoxyphenyl)hydroxycarbene

• Dennis Gerbig,
• David Ley,
• Hans Peter Reisenauer and
• Peter R. Schreiner

Beilstein J. Org. Chem. 2010, 6, 1061–1069, doi:10.3762/bjoc.6.121

• -consistent double-ζ basis set (cc-pVDZ) by utilizing density functional theory (DFT) optimized geometries (M06-2X/cc-pVDZ) with zero-point vibrational energy (ZPVE) corrections. Exchange of the methoxy for a trifluoromethoxy group successfully prevents insertion and (o-trifluoromethoxy)benzaldehyde is

Molecular recognition of organic ammonium ions in solution using synthetic receptors

• Andreas Späth and
• Burkhard König

Beilstein J. Org. Chem. 2010, 6, No. 32, doi:10.3762/bjoc.6.32