Enhanced reactivity of Li⁺@C₆₀ toward thermal [2 + 2] cycloaddition by encapsulated Li⁺ Lewis acid

• Hiroshi Ueno,
• Yu Yamazaki,
• Hiroshi Okada,
• Fuminori Misaizu,
• Ken Kokubo and
• Hidehiro Sakurai

Beilstein J. Org. Chem. 2024, 20, 653–660, doi:10.3762/bjoc.20.58

• +) reference couple. Working electrode: Pt, counter electrode: Pt, reference electrode: Ag/Ag+ in acetonitrile, solvent: o-dichlorobenzene, supporting electrolyte: 50 mM TBAPF6. Reaction mechanisms of thermal and photoinduced [2 + 2] cycloaddition on C60 [19][22][23]. Thermal [2 + 2] reaction of Li+@C60 TFSI

Electron-beam-promoted fullerene dimerization in nanotubes: insights from DFT computations

• Laura Abella,
• Gerard Novell-Leruth,
• Josep M. Ricart,
• Josep M. Poblet and
• Antonio Rodríguez-Fortea

Beilstein J. Org. Chem. 2024, 20, 92–100, doi:10.3762/bjoc.20.10

• singlet state [10]. Although only a few analyses of the reaction mechanisms have been studied due to the complexity of the system, several intermediates inside the CNT have been proposed [3][11][12], which may be different from those proposed to take place in the gas phase or in the solid state at high

• pressures and high temperatures [13][14][15]. We aim to shed light in these reaction mechanisms and energy profiles by using complementary methodologies as standard density functional theory (DFT) calculations and first-principles Car–Parrinello molecular dynamics (CPMD) simulations. Firstly, we have

Beyond n-dopants for organic semiconductors: use of bibenzo[d]imidazoles in UV-promoted dehalogenation reactions of organic halides

• Kan Tang,
• Megan R. Brown,
• Chad Risko,
• Melissa K. Gish,
• Garry Rumbles,
• Phuc H. Pham,
• Oana R. Luca,
• Stephen Barlow and
• Seth R. Marder

Beilstein J. Org. Chem. 2023, 19, 1912–1922, doi:10.3762/bjoc.19.142

• -iodobenzyl chloride. Reaction mechanisms for the reactions of dimeric reductants (D2) such as (Y-DMBI)2 derivatives with acceptors (A) such as organic semiconductors or, in this work, organic halides that react further (the relative rates of steps are indicated for cases where the A reduction potential falls

Recent advancements in iodide/phosphine-mediated photoredox radical reactions

• Tinglan Liu,
• Yu Zhou,
• Junhong Tang and
• Chengming Wang

Beilstein J. Org. Chem. 2023, 19, 1785–1803, doi:10.3762/bjoc.19.131

• advancements in the iodide/phosphine catalytic photoredox system. The primary focus of the paper is to delve into the unique catalytic reactivity exhibited by the iodide/phosphine photoredox system, while also exploring potential reaction mechanisms. It is mainly organized around different types of reactions

Unraveling the role of prenyl side-chain interactions in stabilizing the secondary carbocation in the biosynthesis of variexenol B

• Moe Nakano,
• Rintaro Gemma and
• Hajime Sato

Beilstein J. Org. Chem. 2023, 19, 1503–1510, doi:10.3762/bjoc.19.107

• . Several terpene cyclizations with an exomethylene group are known, such as with caryolene and crotinsulidane diterpenoids, and the reaction mechanisms have been analyzed [27][28][29][30]. It would be interesting to see how the exomethylene group reacts in the cyclization of variexenol B. In this study, we

• follow similar reaction mechanisms, however, when comparing path a and path b, the most striking energy difference is in the step from IM2a/b to IM3a/b (Figure 2B). The energy barrier of this step is 6.3 kcal/mol for path a, whereas 13.6 kcal/mol for path b, with a difference of 7.3 kcal/mol. Although

N-Sulfenylsuccinimide/phthalimide: an alternative sulfenylating reagent in organic transformations

• Fatemeh Doraghi,
• Seyedeh Pegah Aledavoud,
• Mehdi Ghanbarlou,
• Bagher Larijani and
• Mohammad Mahdavi

Beilstein J. Org. Chem. 2023, 19, 1471–1502, doi:10.3762/bjoc.19.106

• is no need to use a metal catalyst, base, or additive. N-(Sulfenyl)succinimide/phthalimide acted as an active electrophilic sulfur source, acted in the reaction mechanisms. However, mechanistic studies need further exploration to define a valid reaction pathway. Therefore, we believe that the use of

Cyclization of 1-aryl-4,4,4-trichlorobut-2-en-1-ones into 3-trichloromethylindan-1-ones in triflic acid

• Vladislav A. Sokolov,
• Andrei A. Golushko,
• Irina A. Boyarskaya and
• Aleksander V. Vasilyev

Beilstein J. Org. Chem. 2023, 19, 1460–1470, doi:10.3762/bjoc.19.105

• , electrophilic properties of atom C3 should be mainly explained by orbital factors, rather than charge ones. Summarizing the data obtained during the synthesis of indanones 3 (Scheme 5, Scheme 6 and Table 1), NMR, and DFT studies on intermediate cations (Table 2 and Table 3), one may propose plausible reaction

• mechanisms for the cyclization of compounds 1 and 2 into indanones 3 in TfOH (Scheme 7). Protonation of the carbonyl oxygen of enone 2 gives rise to cation B which is followed by cyclization into indanone 3 through mesomeric form B'. The hydroxy ketone 1 is protonated at the oxygen atoms leading to cation A

Functionalization of imidazole N-oxide: a recent discovery in organic transformations

• Koustav Singha,
• Imran Habib and
• Mossaraf Hossain

Beilstein J. Org. Chem. 2022, 18, 1575–1588, doi:10.3762/bjoc.18.168

• potent and significant drugs containing imidazole moieties. The formation of imidazole derivatives can be achieved using imidazole N-oxide as starting material. In this review, the scope of substrates and reaction mechanisms of various synthetic approaches using imidazole N-oxides as substrates are

• is a new emerging research area and which offers a lot of room for further development. In this review, several research procedures were discussed with their substrate scope and proposed reaction mechanisms. We hope that this review can be helpful to the researchers and the chemists for the future

Molecular and macromolecular electrochemistry: synthesis, mechanism, and redox properties

• Shinsuke Inagi and
• Mahito Atobe

Beilstein J. Org. Chem. 2022, 18, 1505–1506, doi:10.3762/bjoc.18.158

• macromolecular electrochemistry. The scope of this interdisciplinary issue ranges from synthetic aspects (such as electrosynthesis and reaction mechanisms) to materials science (including redox properties and devices). Shinsuke Inagi and Mahito Atobe Yokohama, October 2022

Make or break: the thermodynamic equilibrium of polyphosphate kinase-catalysed reactions

• Michael Keppler,
• Sandra Moser,
• Henning J. Jessen,
• Christoph Held and
• Jennifer N. Andexer

Beilstein J. Org. Chem. 2022, 18, 1278–1288, doi:10.3762/bjoc.18.134

• the different reaction mechanisms. The thermodynamic equilibrium of the PPK reaction is not as close to the product side as in other ATP regenerating systems, which corresponds to the phosphate transfer potential of the different phosphate donors. This raises the question if PPK/polyP based systems

Experimental and theoretical studies on the synthesis of 1,4,5-trisubstituted pyrrolidine-2,3-diones

• Nguyen Tran Nguyen,
• Vo Viet Dai,
• Nguyen Ngoc Tri,
• Luc Van Meervelt,
• Nguyen Tien Trung and
• Wim Dehaen

Beilstein J. Org. Chem. 2022, 18, 1140–1153, doi:10.3762/bjoc.18.118

• compared to 10ab-v2. Moreover, CH3NH2 approaches 4a/4a’ at the opposite side of the C–C6H5 sites to form IS3/IS5 and finally 10ab-v2/10ab . The reaction mechanisms in the gas phase and in the solvents model are only slightly different. Experimental General experimental methods NMR spectra were acquired on

Understanding the competing pathways leading to hydropyrene and isoelisabethatriene

• Shani Zev,
• Marion Ringel,
• Ronja Driller,
• Bernhard Loll,
• Thomas Brück and
• Dan T. Major

Beilstein J. Org. Chem. 2022, 18, 972–978, doi:10.3762/bjoc.18.97

• reference environment for terpene synthases [10][11][12][15][16][21][22][23][24][25]. The proposed reaction mechanisms yielding HP and IE and are presented in Scheme 1, while the reaction free energy profile is presented in Figure 2. Here, we modeled the transformations A→I (HP) and A’→E’ (IE). The gas

Electroreductive coupling of 2-acylbenzoates with α,β-unsaturated carbonyl compounds: density functional theory study on product selectivity

• Naoki Kise and
• Toshihiko Sakurai

Beilstein J. Org. Chem. 2022, 18, 956–962, doi:10.3762/bjoc.18.95

• attracting much attention, since bioactive compounds possessing these structures are known. This method has the potential to be applied to synthesize bioactive 2-cyanonaphthalen-1-ols [8][9] and 3-substituted phthalides [12][13][14][15][16]. The reaction mechanisms of the electroreductive coupling of 1 with

• by cyclic voltammetry (Table 3) and acceptors 2 revealed no reduction peaks from 0 to −2.00 V vs SCE [5][6]. Therefore, this electroreductive coupling is initiated by the reduction of compounds 1. There are two possible reaction mechanisms for the reductive coupling of 1 with 2a as illustrated in

Structural basis for endoperoxide-forming oxygenases

• Takahiro Mori and
• Ikuro Abe

Beilstein J. Org. Chem. 2022, 18, 707–721, doi:10.3762/bjoc.18.71

• attention in the field of natural products and organic synthesis. In this review, we summarize the structural analyses, mechanistic investigations, and proposed reaction mechanisms of endoperoxide-forming oxygenases, including cyclooxygenase, fumitremorgin B endoperoxidase (FtmOx1), and the asnovolin A

• reduced to produce PGH2. PGH2 is metabolized by downstream enzymes to yield a series of prostaglandins, which play important roles in inflammatory responses [35][36][37]. Although the active site architectures of COX-1 and COX-2 are not completely identical, the reaction mechanisms and catalytic residues

• enzymes, COX, FtmOx1, and NvfI, indicated that these enzymes employ distinct reaction mechanisms, suggesting that the enzymatic endoperoxide formation reactions individually evolve in a substrate-dependent manner. This fact makes it difficult to identify the endoperoxide-forming enzymes by a sequence

Tri(n-butyl)phosphine-promoted domino reaction for the efficient construction of spiro[cyclohexane-1,3'-indolines] and spiro[indoline-3,2'-furan-3',3''-indolines]

• Hui Zheng,
• Ying Han,
• Jing Sun and
• Chao-Guo Yan

Beilstein J. Org. Chem. 2022, 18, 669–679, doi:10.3762/bjoc.18.68

• to give selectively spiro[indoline-3,2'-furan-3',3''-indolines] in satisfactory yields. The relative configuration of the complex spirooxindoles was confirmed by determination of several single crystal structures. Also, plausible reaction mechanisms have been proposed. This reaction has the

Menadione: a platform and a target to valuable compounds synthesis

• Acácio S. de Souza,
• Ruan Carlos B. Ribeiro,
• Dora C. S. Costa,
• Fernanda P. Pauli,
• David R. Pinho,
• Matheus G. de Moraes,
• Fernando de C. da Silva,
• Luana da S. M. Forezi and
• Vitor F. Ferreira

Beilstein J. Org. Chem. 2022, 18, 381–419, doi:10.3762/bjoc.18.43

• reaction mechanisms: free radical autoxidation, cation radical autoxidation, and thermal intersystem crossing (ISC), using 18O2 labeling, spin-trapping, spectroscopic, mass spectrometric, kinetic, and computational techniques. After several experiments, the obtained results have demonstrated that the 2

Recent advances in the tandem annulation of 1,3-enynes to functionalized pyridine and pyrrole derivatives

• Yi Liu,
• Puying Luo,
• Yang Fu,
• Tianxin Hao,
• Xuan Liu,
• Qiuping Ding and
• Yiyuan Peng

Beilstein J. Org. Chem. 2021, 17, 2462–2476, doi:10.3762/bjoc.17.163

• introduce the applications of the products and the reaction mechanisms for the synthesis of corresponding N-heterocycles. Keywords: 1,3-enyne; functionalization; pyridine; pyrrole; tandem annulation; Introduction The pyridine moiety is an important class of six-membered N-heterocycles that is widely found

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

On the application of 3d metals for C–H activation toward bioactive compounds: The key step for the synthesis of silver bullets

• Renato L. Carvalho,
• Amanda S. de Miranda,
• Mateus P. Nunes,
• Roberto S. Gomes,
• Guilherme A. M. Jardim and
• Eufrânio N. da Silva Júnior

Beilstein J. Org. Chem. 2021, 17, 1849–1938, doi:10.3762/bjoc.17.126

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

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

• these products in academia, pharmacy, and industry. This overview summarizes the latest advances in the synthesis of fully decorated triazoles. In many cases, the reaction mechanisms of triazole formation have been discussed. The current overview can serve as a base for future advancements in modern

[2 + 1] Cycloaddition reactions of fullerene C₆₀ based on diazo compounds

• Yuliya N. Biglova

Beilstein J. Org. Chem. 2021, 17, 630–670, doi:10.3762/bjoc.17.55

• synthetic organic chemists as it allows to obtain methanofullerenes, fullerenoaziridines, or fullerenooxyranes. These reactions can involve, for example, the addition of stabilized carbanions, carbenes, and nitrenes and can involve various reaction mechanisms. While in the early years of intense research on

On the mass spectrometric fragmentations of the bacterial sesterterpenes sestermobaraenes A–C

• Anwei Hou and
• Jeroen S. Dickschat

Beilstein J. Org. Chem. 2020, 16, 2807–2819, doi:10.3762/bjoc.16.231

• investigation of the electron impact mass spectrometry (EIMS) fragmentation reactions of these sesterterpene hydrocarbons. Keywords: isotopes; mass spectrometry; reaction mechanisms; sesterterpenes; Streptomyces mobaraensis; Introduction The sestermobaraenes A–F (1–6) and sestermobaraol (7) are a series of

• terpene fragmentations in EIMS in the future by the strategy applied in this work to learn more about the underlying reaction mechanisms. Experimental Preparation of 13C-labelled compounds 1–3 and GC–MS analysis The 25 isotopomers of (13C)-1, (13C)-2, and (13C)-3 were prepared enzymatically with SmTS1

Photosensitized direct C–H fluorination and trifluoromethylation in organic synthesis

• Shahboz Yakubov and
• Joshua P. Barham

Beilstein J. Org. Chem. 2020, 16, 2151–2192, doi:10.3762/bjoc.16.183

Synthesis, docking study and biological evaluation of ᴅ-fructofuranosyl and ᴅ-tagatofuranosyl sulfones as potential inhibitors of the mycobacterial galactan synthesis targeting the galactofuranosyltransferase GlfT2

• Marek Baráth,
• Jana Jakubčinová,
• Zuzana Konyariková,
• Stanislav Kozmon,
• Katarína Mikušová and
• Maroš Bella

Beilstein J. Org. Chem. 2020, 16, 1853–1862, doi:10.3762/bjoc.16.152

• mechanism studies using computational chemistry methods. The probable reaction mechanisms were studied by hybrid DFT QM/MM molecular dynamics simulations [11] where the possible transition state (TS) structures were localized. The observation of the possible TS structure opens the opportunities for the in