Site-selective reactions mediated by molecular containers

• Rui Wang and
• Yang Yu

Beilstein J. Org. Chem. 2022, 18, 309–324, doi:10.3762/bjoc.18.35

• (Figure 1c). This kind of unusual site-selectivity originated from the fixed orientation of the guest substrates confined to the cage host A before the reaction. Force-field calculations showed that the guest substrates 1 and 2 were parallel to each other with the double bond of 2 in close contact with

• reactions. Naphthalene is usually hard to undergo Diels–Alder reactions [44][45][46], even though the quantum-mechanical and thermochemical calculations suggest that the reaction is exothermic, which indicates the entropic cost is significant [47]. In 2010, the same group reported another interesting site

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

• density functional theory calculations. We set out to confirm the catalytic cycle in detail, the geometries of the intermediates, the energy profiles of the reactions, and most importantly, the origin of regioselectivity. Results and Discussion Experimental We began our investigation with C1-methyl

• 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

• optimization and frequency calculations. Frequency analyses and single-point energies were calculated with the M06 functional [69] with the triple-ζ basis set def2TZVP [70] with the PCM (1,4-dioxane) solvent model [72]. The Gibbs free energies of formation of the reactants, products, and transition states were

1,2-Naphthoquinone-4-sulfonic acid salts in organic synthesis

• Ruan Carlos B. Ribeiro,
• Patricia G. Ferreira,
• Amanda de A. Borges,
• Luana da S. M. Forezi,
• Fernando de Carvalho da Silva and
• Vitor F. Ferreira

Beilstein J. Org. Chem. 2022, 18, 53–69, doi:10.3762/bjoc.18.5

• equilibrium between A and B using semiempirical calculations (AM1 and PM3) and DFT (B3LYP/6-31G(d)) in the gas phase and water, where it was observed that in the gas phase B is the most stable, while in water A is formed, which is in agreement with the experimental results reported in the literature. There

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

• calculations; enzyme mechanisms; isotopes; terpenes; Introduction Patchouli oil, the essential oil of the shrub Pogostemon cablin, has a pleasant woody odour and is of high economic value for the perfumery and cosmetics industries. It is mainly composed of sesquiterpenes with patchoulol as the main compound

• contradictory. For this reason, we have reinvestigated the enzyme mechanism of PTS in isotopic labelling experiments through methods recently developed in our laboratory that make use of 13C and 2H-substituted terpene precursors, and by DFT calculations. The general strategy in these experiments is to use

• experiments and the DFT calculations were not only carried out in a way to gain support for one mechanism, but also to disprove some of the earlier reports in order to resolve the contradictions in the literature. Results and Discussion Absolute configurations of patchoulol and pogostol In order to

Peptide stapling by late-stage Suzuki–Miyaura cross-coupling

• Hendrik Gruß,
• Rebecca C. Feiner,
• Ridhiwan Mseya,
• David C. Schröder,
• Michał Jewgiński,
• Kristian M. Müller,
• Rafał Latajka,
• Antoine Marion and
• Norbert Sewald

Beilstein J. Org. Chem. 2022, 18, 1–12, doi:10.3762/bjoc.18.1

• in i + 4-position of the linear axin CBD sequence aAxWt were substituted by tryptophan and lysine, respectively, to have a higher analogy to the lysine modified SMC stapled peptides. Following the indications of DFT calculations, stapled peptide P5 was synthesised by modification of lysine in the i

• for support in the synthetic work. Funding The project was supported in part by a Bielefeld University Ph.D. fellowship to H.G. and by Deutsche Forschungsgemeinschaft (SE609/16-1). The DFT calculations were carried out using hardware and software resources of the Supercomputing and Networking Center

• in Wroclaw (grant no. 197). R.M. and A.M. gratefully acknowledge the support of NVIDIA Corporation with the donation of a Titan Xp GPU used for this research as well as TUBITAK ULAKBIM High Performance and Grid Computing Center (TRUBA resources) for additional calculations.

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

• HAT step energetics and determined an optimized geometry for the transition state, showing that the hydrogen atom transfer between aldehydes and DABCO is a mildly endergonic, yet sufficiently fast step. The same calculations were performed with quinuclidine, for comparison of both catalysts and 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

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

• DICzTRZ were determined by a combination of NMR spectroscopy, mass spectrometry, and IR spectroscopy. Theoretical calculations Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations in the gas phase at the PBE0/6-31G(d,p) level reveal the potential of DICzTRZ as a TADF material. The

• , respectively, while the S1 level for DICzTRZ is more stabilized at 2.80 eV vs 2.94 eV for ICzTRZ). We can clearly observe that the phosphorescence spectrum presents a well-defined structure, typical for transitions coming from a local excited (LE) type state on the diindolocarbazole. TDA-DFT calculations in

• calculations showed a much larger density of triplet states, which suggests that RISC will be faster in this compound compared to its parent. The twin design strategy leads to an enhancement in the molar extinction coefficient of the low-lying CT states, accompanied by a red-shift in the emission. The 20 wt

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

• , C. tropicalis, and C. glabrata standard strains. A deep conformational survey was monitored using DFT calculations with the aim to explain the importance of the final conformation in the biological experimental results. Keywords: antituberculosis; bidentate ligands; DFT; nickel; palladium

• results of its corresponding nickel(II) [18] and palladium(II) [19][20] complexes with the analogous tests obtained in the case of having a benzylic substituent at the same position. Also, DFT calculations are run in order to study the conformational analysis of the synthetized complexes. Results and

• 62.50–125 μg/mL (Table 2) when compared to reference drugs. the L3-Ni complex has the highest activity against Candida glabrata. DFT calculations of complexes The survey of relationship between structure of the complex and activity (SAR) moved us to design DFT calculations. The difference of the

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

• functional calculations showed that the chiral phosphoric acid proton forms an H-bond with nitrogen atoms of 1 and the phosphate acts as a chiral counterion, resulting in a [3,3]-sigmatropic rearrangement with controlled stereoselectivity [14][41]. In 2017, Tan and co-workers developed an organocatalytic

• density functional theory calculations [46]. Recently, Shi, Lin and co-workers reported the atroposelective synthesis of axially chiral biaryls by Pd(II)-catalyzed free amine-directed atroposelective C–H olefination using chiral spirophosphoric acid CPA 5 as an efficient ligand and Ag2CO3 as the oxidant

• provide easy access to the privileged NOBIN (2-amino-2’-hydroxy-1,1’-binaphthyl) structures 41. The additional insights into the origins of enantiocontrol were described by DFT calculations. Owing to the presence of axially chiral indole-based biaryl scaffolds such as naphthylindoles and phenylindoles in

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

• influence on the catalytic reactions. Under ball-milling conditions, the Michael adducts were obtained in good yields but with slightly lower enantiomeric purities than in solution. DFT calculations elucidated its mode of action and confirmed a dual activation mode, which combines enamine activation of

• have evaluated the suitability of these catalysts under solvent-free conditions. With the help of DFT calculations, we elucidated the mode of action of these catalysts. Results and Discussion Synthesis of catalysts We have started the synthesis of the catalysts from Boc-protected (S)-prolinol (1), from

• 8f in 76 and 79% yield with comparable diastereoselectivity and enantioselectivity (Table 4, entries 8 and 9). DFT calculations of catalyst structure and reaction stereo-course To understand the catalyst operation, we have conducted DFT calculations of its structure and reaction course. All

Recent advances in organocatalytic asymmetric aza-Michael reactions of amines and amides

• Pratibha Sharma,
• Raakhi Gupta and
• Raj K. Bansal

Beilstein J. Org. Chem. 2021, 17, 2585–2610, doi:10.3762/bjoc.17.173

• enantioselectivity (47–98% ee). The observed results were rationalized with density functional theory calculations (Table 8) [42]. 1.3 Reactions catalyzed by chiral amines He and co-workers developed heterogeneous synergistic catalysis using chiral amines SBA-15 (cat. 44), which promote aza-Michael–Henry cascade

Synthesis and investigation on optical and electrochemical properties of 2,4-diaryl-9-chloro-5,6,7,8-tetrahydroacridines

• Najeh Tka,
• Mohamed Adnene Hadj Ayed,
• Mourad Ben Braiek,
• Mahjoub Jabli and
• Peter Langer

Beilstein J. Org. Chem. 2021, 17, 2450–2461, doi:10.3762/bjoc.17.162

• their HOMO/LUMO energy levels were estimated by cyclic voltammetry measurements. Besides, density functional theory calculations were carried out for further exploration of their electronic properties. Keywords: catalysis; cross-coupling; cyclization; fluorescence; palladium; Introduction π-Conjugated

• and their optical and electrochemical properties investigation by the use of UV–vis and emission spectroscopy, CV measurements as well as DFT calculations. Results and Discussion Synthesis. At the beginning of this study, we synthesized 2,4-dibromo-9-chloro-5,6,7,8-tetrahydroacridine (2) by refluxing

• further study the electronic properties, DFT calculations were carried out on the fully ground state at the restricted B3LYPlevel with 6-31G(d) basis set using dichloromethane as a continuum solvent model. The optimized chemical structures of 4a–d are given in Figure 7 with selected geometrical parameters

Synthesis of 5-arylacetylenyl-1,2,4-oxadiazoles and their transformations under superelectrophilic activation conditions

• Andrey I. Puzanov,
• Dmitry S. Ryabukhin,
• Anna S. Zalivatskaya,
• Dmitriy N. Zakusilo,
• Darya S. Mikson,
• Irina A. Boyarskaya and
• Aleksander V. Vasilyev

Beilstein J. Org. Chem. 2021, 17, 2417–2424, doi:10.3762/bjoc.17.158

• bond of these oxadiazoles quantitatively resulted in E/Z-vinyl triflates. The reactions of the cationic intermediates have been studied by DFT calculations and the reaction mechanisms are discussed. Keywords: acetylene-oxadiazoles; Friedel–Crafts reaction; hydroarylation; superelectrophilic activation

• expect the formation of similar dications at the protonation of acetylenyloxadiazoles 3 in Brønsted superacids (see Table 1). Table 1 contains data on DFT calculations of cations Aa–d (N-protonated forms) and Ba–d (N,C-diprotonated forms) derived at the protonation of oxadiazoles 3a–d. Charge

• positive charge (0.40–0.47 e) and gives a big contribution into LUMO (16.7–30%), pointing out that this carbon is a reactive electrophilic center by charge and orbital factors. Thus, according our previous data on reactions of 5-styryl-1,2,4-oxadiazoles 1 [24] and results of the DFT calculations for

Strategies for the synthesis of brevipolides

• Yudhi D. Kurniawan and
• A'liyatur Rosyidah

Beilstein J. Org. Chem. 2021, 17, 2399–2416, doi:10.3762/bjoc.17.157

• comprehensive combination of quantum mechanical calculations and experimental spectroscopic analysis of their NMR and ECD data, to have a unique tetrahydrofuran ring instead of the cyclopropane functionality. The absolute configuration of these five compounds were evaluated and all conserved as C6R, C1’S, C2’R

Halides as versatile anions in asymmetric anion-binding organocatalysis

• Lukas Schifferer,
• Martin Stinglhamer,
• Kirandeep Kaur and
• Olga García Macheño

Beilstein J. Org. Chem. 2021, 17, 2270–2286, doi:10.3762/bjoc.17.145

• example highlighting the importance of sidechain catalyst design was given by Jacobsen et al. in the tail-to-head cyclization of neryl chloride and derivatives 59 (Scheme 13) [17]. Mechanistic studies and DFT calculations revealed that an extended π-system in the sidechain of the bidentate urea catalyst

(Phenylamino)pyrimidine-1,2,3-triazole derivatives as analogs of imatinib: searching for novel compounds against chronic myeloid leukemia

• Luiz Claudio Ferreira Pimentel,
• Lucas Villas Boas Hoelz,
• Henayle Fernandes Canzian,
• Frederico Silva Castelo Branco,
• Andressa Paula de Oliveira,
• Vinicius Rangel Campos,
• Floriano Paes Silva Júnior,
• Rafael Ferreira Dantas,
• Jackson Antônio Lamounier Camargos Resende,
• Anna Claudia Cunha,
• Nubia Boechat and
• Mônica Macedo Bastos

Beilstein J. Org. Chem. 2021, 17, 2260–2269, doi:10.3762/bjoc.17.144

• used in all calculations. The final R1 was 0.1284 (I >2σ(I)), and wR2 was 0.3858 (all data). Cell line and cell culture All novel compounds synthesized (1a,b, and 2a–j) were evaluated for their activity against K562 cells (ATCC® CRL-243TM), a CML cell line, and a WSS-1 healthy cell line (ATCC® CRL

Nomimicins B–D, new tetronate-class polyketides from a marine-derived actinomycete of the genus Actinomadura

• Zhiwei Zhang,
• Tao Zhou,
• Taehui Yang,
• Keisuke Fukaya,
• Enjuro Harunari,
• Shun Saito,
• Katsuhisa Yamada,
• Chiaki Imada,
• Daisuke Urabe and
• Yasuhiro Igarashi

Beilstein J. Org. Chem. 2021, 17, 2194–2202, doi:10.3762/bjoc.17.141

• (Δε) 208 (−4.98), 244 (+3.85), 298 nm (−1.09); IR νmax: 3348, 2938, 1735, 1620, 1435, 997 cm−1; HRESITOFMS (m/z): [M + Na]+ calcd for C30H40O6Na, 519.2717; found, 519.2722. ECD calculations The conformational sampling of structure 4a was performed by applying 100,000 steps of the Monte Carlo Multiple

• calculations were carried out at the same level of theory to confirm the absence of imaginary frequencies and obtain thermal corrections for the Gibbs free energy. After eliminating duplicated structures with the threshold of 0.01 Å RMSD, the single-point energy was calculated at the M06-2X/def2-TZVP-SMD level

Development of N-F fluorinating agents and their fluorinations: Historical perspective

• Teruo Umemoto,
• Yuhao Yang and
• Gerald B. Hammond

Beilstein J. Org. Chem. 2021, 17, 1752–1813, doi:10.3762/bjoc.17.123

Sustainable manganese catalysis for late-stage C–H functionalization of bioactive structural motifs

• Jongwoo Son

Beilstein J. Org. Chem. 2021, 17, 1733–1751, doi:10.3762/bjoc.17.122

• . Additionally, difluorination was observed with negligible amounts because the monofluorinated product is rendered more electronically deficient by the first fluorine atom. Based on an analysis by DFT calculations, the postulated reaction pathway of manganese-catalyzed C–H fluorination is described in Figure 1

Electron-rich triarylphosphines as nucleophilic catalysts for oxa-Michael reactions

• Susanne M. Fischer,
• Simon Renner,
• A. Daniel Boese and
• Christian Slugovc

Beilstein J. Org. Chem. 2021, 17, 1689–1697, doi:10.3762/bjoc.17.117

• calculations by an increasing stationary concentration of the primary reaction product, the corresponding β-phosphonium α-carbanionic zwitterion, when using arylphosphines with more electron-donating substituents. Besides the catalyst, the second decisive factor for the speed of the reaction is the acidity of

• from MZ-Gel SD plus, 500 A and 100 A, linear 5 µ; UV detector (SPD-20A) and RI detector (RID-20A)) using THF as eluent. Poly(styrene) standards in the range of 350 to 17800 g/mol purchased from Polymer Standard Service were used for calibration. Computational details All calculations were run with the

• calculations, temperature effects (298 K) and zero-point energies have been approximated by the rigid-rotor-harmonic oscillator (RRHO) approximation. The zero-point energies have been scaled by a factor of 1.0030 (B3LYP/def2-TZVPPD) and 1.0302 (PBE/def2-SVPD) to account for anharmonic effects [52]. Solvent

2,4-Bis(arylethynyl)-9-chloro-5,6,7,8-tetrahydroacridines: synthesis and photophysical properties

• Najeh Tka,
• Mohamed Adnene Hadj Ayed,
• Mourad Ben Braiek,
• Mahjoub Jabli,
• Noureddine Chaaben,
• Kamel Alimi,
• Stefan Jopp and
• Peter Langer

Beilstein J. Org. Chem. 2021, 17, 1629–1640, doi:10.3762/bjoc.17.115

• . In order to elucidate these experimental observations, quantum chemical calculations based on density functional theory (DFT) methodology were performed. The estimated visualization of highest occupied and lowest unoccupied molecular orbitals, as well as the molecular electrostatic potential (MEP) of

• were recorded on a Shimadzu 2401 PC spectrophotometer in quartz cuvettes with a path length of 1 cm. Emission spectra were recorded on a Perkin-Elmer LS50B spectrofluorimeter. Theoretical calculations Theoretical studies were realized in vacuum with Gaussian 09 program [72]. The geometry of the

A recent overview on the synthesis of 1,4,5-trisubstituted 1,2,3-triazoles

• Pezhman Shiri,
• Ali Mohammad Amani and
• Thomas Mayer-Gall

Beilstein J. Org. Chem. 2021, 17, 1600–1628, doi:10.3762/bjoc.17.114

• investigated by means of DFT calculations using the reaction between enaminone 6a and phenyl azide. TS1 and TS2 have been proposed as two transition states, which then converted to IN1 and IN2 as two possible isomers. The stable final products were achieved via a cascade reaction including the elimination of

Recent advances in the application of isoindigo derivatives in materials chemistry

• Andrei V. Bogdanov and
• Vladimir F. Mironov

Beilstein J. Org. Chem. 2021, 17, 1533–1564, doi:10.3762/bjoc.17.111

• the efficiency from 4.58 to 6.21%. Based on the data of quantum chemical calculations, Park et al. [34] showed that in the fluorinated derivative, the dihedral angle between the thiophene rings is 0.88° (for comparison, in compound 22a it is 17.55°), which provides better planarity of the polymer and

Free-radical cyclization approach to polyheterocycles containing pyrrole and pyridine rings

• Ivan P. Mosiagin,
• Olesya A. Tomashenko,
• Dar’ya V. Spiridonova,
• Mikhail S. Novikov,
• Sergey P. Tunik and
• Alexander F. Khlebnikov

Beilstein J. Org. Chem. 2021, 17, 1490–1498, doi:10.3762/bjoc.17.105

• complexes, Au(I) [20], Ir(III) [21] and Eu(III) [22] (Scheme 1). According to the calculations, the isomeric pyrido[2,1-a]pyrrolo[3,4-c]isoquinoline system B (Scheme 1) should have no less interesting photophysical properties [17], than skeleton A but its synthesis is still a challenge. In particular

Double-headed nucleosides: Synthesis and applications

• Vineet Verma,
• Jyotirmoy Maity,
• Vipin K. Maikhuri,
• Ritika Sharma,
• Himal K. Ganguly and
• Ashok K. Prasad

Beilstein J. Org. Chem. 2021, 17, 1392–1439, doi:10.3762/bjoc.17.98