Catalytic multi-step domino and one-pot reactions

• Svetlana B. Tsogoeva

Beilstein J. Org. Chem. 2024, 20, 254–256, doi:10.3762/bjoc.20.25

• through concerted or stepwise mechanisms. An enantioselective palladium-catalyzed three-component reaction of glyoxylic acid, sulfonamides, and aryltrifluoroborates toward synthetically useful α-arylglycine compounds is described by the Manolikakes group [11]. Moreover, Šebesta and co-workers report a

Photochromic derivatives of indigo: historical overview of development, challenges and applications

• Gökhan Kaplan,
• Zeynel Seferoğlu and
• Daria V. Berdnikova

Beilstein J. Org. Chem. 2024, 20, 228–242, doi:10.3762/bjoc.20.23

• thermal half-lives of the photoisomers range from seconds to days. Detailed photophysical and photochemical studies have provided insight into the photoswitching mechanisms of indigo derivatives and enabled control of their photochemical properties through targeted design of the molecular structure. The

Photoinduced in situ generation of DNA-targeting ligands: DNA-binding and DNA-photodamaging properties of benzo[c]quinolizinium ions

• Julika Schlosser,
• Olga Fedorova,
• Yuri Fedorov and
• Heiko Ihmels

Beilstein J. Org. Chem. 2024, 20, 101–117, doi:10.3762/bjoc.20.11

• ]quinolizinium ions 3b–g (yields in % refer to isolated products). Proposed mechanisms for the photoinduced DNA damage initiated by photoexcitation of benzoquinolizinium 3f. Absorption and emission maxima of 3c–g in the absence and presence of ct DNA and binding constants of their complexes with ct DNA. Gel

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

• -zero intercept, a behavior which conforms with a rate law consisting of the sum of two terms, one first order in [D2] and one first order in both [D2] and [RX] and is similar to doping behavior we have recently seen for some weakly bonded dimers where both “cleavage-first” and “ET-first” mechanisms are

• -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

Anion–π catalysis on carbon allotropes

• M. Ángeles Gutiérrez López,
• Mei-Ling Tan,
• Giacomo Renno,
• Augustina Jozeliūnaitė,
• J. Jonathan Nué-Martinez,
• Javier Lopez-Andarias,
• Naomi Sakai and
• Stefan Matile

Beilstein J. Org. Chem. 2023, 19, 1881–1894, doi:10.3762/bjoc.19.140

• consistent with the existence of OEEF catalysis with a destabilized transition state XIX. It also disfavored contributions from SN1-type mechanisms and, most important, from electron transfer. Anion–π catalysis on graphite Beginning with spherical fullerenes, expansion of the aromatic surface of carbon

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

• -involved reactions is crucial for gaining a deeper understanding of their underlying mechanisms and expediting the process of designing new reactions. Overall, addressing these challenges and advancing the field through innovative approaches and mechanistic insights will contribute to the continued

Quinoxaline derivatives as attractive electron-transporting materials

• Zeeshan Abid,
• Liaqat Ali,
• Sughra Gulzar,
• Faiza Wahad,
• Raja Shahid Ashraf and
• Christian B. Nielsen

Beilstein J. Org. Chem. 2023, 19, 1694–1712, doi:10.3762/bjoc.19.124

• should focus on understanding degradation mechanisms, developing effective device encapsulation strategies, and ensuring environmental compatibility to guarantee sustained performance and viability in commercial applications. Additionally, scalability and cost-effective manufacturing processes are key

Benzoimidazolium-derived dimeric and hydride n-dopants for organic electron-transport materials: impact of substitution on structures, electrochemistry, and reactivity

• Swagat K. Mohapatra,
• Khaled Al Kurdi,
• Samik Jhulki,
• Georgii Bogdanov,
• John Bacsa,
• Maxwell Conte,
• Tatiana V. Timofeeva,
• Seth R. Marder and
• Stephen Barlow

Beilstein J. Org. Chem. 2023, 19, 1651–1663, doi:10.3762/bjoc.19.121

• by various quinone derivatives [63]. For both mechanisms, the first steps are typically rate determining and thus, in general, the rate law is: where k1 and k2 are rate constants for the first steps of the “cleavage first” and “ET-first” pathways respectively, k1 being negligible in the case of

• the rise in VII•– absorption is neither zero-order nor first-order in VII, consistent with both mechanisms contributing, as previously demonstrated by more extensive investigations in the case of 1c2, 1d2, and (RhCp*Cp)2 [14][61]. Thus, the Y = alkyl derivative (1h2, “ET-first” only) appears to be

• more strongly bonded than its Y = aryl counterparts (1b2, 1g2, both mechanisms), consistent with previous DFT calculations for 1b2 and 1e2 (ΔUdiss = 163 and 210 kJ mol–1, respectively) and with the expected impact of the different Y substituents on monomer radical stability. In addition, the reaction

Sulfur-containing spiroketals from Breynia disticha and evaluations of their anti-inflammatory effect

• Ken-ichi Nakashima,
• Naohito Abe,
• Masayoshi Oyama,
• Hiroko Murata and
• Makoto Inoue

Beilstein J. Org. Chem. 2023, 19, 1604–1614, doi:10.3762/bjoc.19.117

• Freund's adjuvant-induced arthritis in rats [12]. However, the molecular mechanisms of these anti-inflammatory effects have not been investigated. In our ongoing search for bioactive natural products, we have isolated three new spiroketals – breynin J (1), epibreynin J (2), and probreynogenin (3) – and

Radical chemistry in polymer science: an overview and recent advances

• Zixiao Wang,
• Feichen Cui,
• Yang Sui and
• Jiajun Yan

Beilstein J. Org. Chem. 2023, 19, 1580–1603, doi:10.3762/bjoc.19.116

• considered to have two mechanisms, degenerative transfer and reversible termination, which are comparable to RAFT and NMP, respectively (Scheme 7) [70]. Iodine transfer polymerization (ITP) is also a commonly used degenerate chain-transfer method. Its origin can be traced back to the 1970s [71] and it is

• using benzophenone. Depolymerization mechanism of common photoresists. (a) A possible mechanism of radiation decomposition of poly(methyl methacrylate). (b) A proposed mechanism of simultaneous radical/cationic decomposition of poly(olefin sulfone) upon radiation [197]. Proposed mechanisms of

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

• 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

• -4,4,4-trichlorobut-2-en-1-ones 2 into 3-trichloromethylindan-1-ones 3 in TfOH. Cyclization of 1-aryl-4,4,4-trichloro-3-hydroxybutan-1-ones 1 into 3-trichloromethylindan-1-ones 3 in TfOH. Plausible mechanisms for the cyclization of compounds 1 and 2 into indanones 3 in TfOH. Transformations of hydroxy

Synthesis of ether lipids: natural compounds and analogues

• Marco Antônio G. B. Gomes,
• Alicia Bauduin,
• Chloé Le Roux,
• Romain Fouinneteau,
• Wilfried Berthe,
• Mathieu Berchel,
• Hélène Couthon and
• Paul-Alain Jaffrès

Beilstein J. Org. Chem. 2023, 19, 1299–1369, doi:10.3762/bjoc.19.96

• modulation of membrane proteins that represent a pertinent strategy for some diseases like cancers. Beside the use of synthetic ether lipids for the prevention or the treatment of cancers via different mechanisms, it must be noted that some synthetic ether lipids (e.g., Ino-C2-PAF) have also the ability to

Non-noble metal-catalyzed cross-dehydrogenation coupling (CDC) involving ether α-C(sp³)–H to construct C–C bonds

• Hui Yu and
• Feng Xu

Beilstein J. Org. Chem. 2023, 19, 1259–1288, doi:10.3762/bjoc.19.94

• Cu-catalyzed oxidative coupling reactions [43]. However, due to complex mechanisms, Cu-catalyzed C–H functionalization reactions developed only slowly in the last decade. Since recently the Cu-catalyzed oxidative coupling has emerged as a powerful synthetic strategy due to the development of CDC

• metal-triggered oxidation of the ether substrate to obtain the corresponding radical or oxonium ion as the key intermediate to obtain the final coupling product. Subsequently, some novel Co-catalyzed coupling mechanisms have been proposed. In 2016, Lu et al. reported that the Co/TBHP catalyst oxidation

Enabling artificial photosynthesis systems with molecular recycling: A review of photo- and electrochemical methods for regenerating organic sacrificial electron donors

• Grace A. Lowe

Beilstein J. Org. Chem. 2023, 19, 1198–1215, doi:10.3762/bjoc.19.88

• photosynthesis research not only because they occur in biological photosynthesis but also because the PCET can circumvent unstable one electron-reduced intermediates. This makes PCET mechanisms well-suited for complex multielectron reactions required to transfer electrons and protons from water onto carbon

Exploring the role of halogen bonding in iodonium ylides: insights into unexpected reactivity and reaction control

• Carlee A. Montgomery and
• Graham K. Murphy

Beilstein J. Org. Chem. 2023, 19, 1171–1190, doi:10.3762/bjoc.19.86

• provides an overview of the reactions of iodonium ylides in which halogen bonding has been invoked. Herein, we summarize key discoveries and mechanistic proposals from the early iodonium ylide literature that invoked halogen bonding-type mechanisms, as well as recent reports of reactions between iodonium

• cyclopropane 22a. Interestingly, Hadjiarapoglou also revisited their investigation of iodonium ylide cycloadditions and their associated mechanisms [120], using diphenylketene as a new reaction partner with dimedone iodonium ylide 6 (analogous to earlier work reported by Koser in 1975 [9]). Investigations by

• , their scope has recently expanded to include X–H insertions based on single electron transfer (SET) mechanisms, cycloadditions based on blue LED photochemistry and radiofluorinations of unactivated arene motifs. In these reports, mechanistic proposals commonly treat the hypervalent iodine atom as being

Photoredox catalysis harvesting multiple photon or electrochemical energies

• Mattia Lepori,
• Simon Schmid and
• Joshua P. Barham

Beilstein J. Org. Chem. 2023, 19, 1055–1145, doi:10.3762/bjoc.19.81

The effect of dark states on the intersystem crossing and thermally activated delayed fluorescence of naphthalimide-phenothiazine dyads

• Liyuan Cao,
• Xi Liu,
• Xue Zhang,
• Jianzhang Zhao,
• Fabiao Yu and
• Yan Wan

Beilstein J. Org. Chem. 2023, 19, 1028–1046, doi:10.3762/bjoc.19.79

• intersystem crossing (rISC) is slow, without coupling with an approximate 3LE state. These studies are useful for an in-depth understanding of the photophysical mechanisms of the TADF emitters, as well as for molecular structure design of new electron donor–acceptor TADF emitters. Keywords: charge-transfer

• [38][39][40][41][42][43][44] and, more recently, time-resolved electron paramagnetic resonance (TREPR) spectroscopy [33][39][44][45][46] were also applied to study TADF mechanisms, but the examples are limited. Therefore, much room is left for studies of the photophysical mechanism of the TADF

• state energy), while keeping other factors intact to a large extent (e.g., the LE state energy). This is an important advantage for the study of complicated photophysical mechanisms involved in TADF processes. The syntheses of the dyads are based on the known derivatization chemistry of NI and PTZ

Intermediates and shunt products of massiliachelin biosynthesis in Massilia sp. NR 4-1

• Till Steinmetz,
• Blaise Kimbadi Lombe and
• Markus Nett

Beilstein J. Org. Chem. 2023, 19, 909–917, doi:10.3762/bjoc.19.69

• into the cell through membrane receptors and transporters. Eventually, the bound metal is released through reductive or hydrolytic mechanisms [2]. In the past years, β-proteobacteria have received increasing attention as producers of siderophores with interesting chemical features. For instance

• underlie discrete regulation mechanisms, which explains their context-dependent production [27]. The examples of P. aeruginosa and B. anthracis suggest that siderophore biosynthesis sometimes requires specific triggers beyond iron deficiency, which may not be met under laboratory conditions. The six

Light-responsive rotaxane-based materials: inducing motion in the solid state

• Adrian Saura-Sanmartin

Beilstein J. Org. Chem. 2023, 19, 873–880, doi:10.3762/bjoc.19.64

• Photoresponsive rotaxane discrete crystals A complete understanding of the crystallization mechanisms accompanied by a rational design can lead to the obtention of crystalline molecular materials which allow the dynamics of the counterparts to take place [35][36][37]. Indeed, the motion of the cyclic counterparts

Pyridine C(sp²)–H bond functionalization under transition-metal and rare earth metal catalysis

• Haritha Sindhe,
• Malladi Mounika Reddy,
• Karthikeyan Rajkumar,
• Akshay Kamble,
• Amardeep Singh,
• Anand Kumar and
• Satyasheel Sharma

Beilstein J. Org. Chem. 2023, 19, 820–863, doi:10.3762/bjoc.19.62

• the mechanisms involved. Keywords: C–H functionalization; heterocycles; pyridine; rare earth metal; transition-metal-catalyzed; Introduction Pyridine, one of the most important azaheterocyclic scaffolds, is found in a diverse range of bioactive natural products, pharmaceuticals, and functional

Synthesis of substituted 8H-benzo[h]pyrano[2,3-f]quinazolin-8-ones via photochemical 6π-electrocyclization of pyrimidines containing an allomaltol fragment

• Constantine V. Milyutin,
• Andrey N. Komogortsev,
• Boris V. Lichitsky,
• Mikhail E. Minyaev and
• Valeriya G. Melekhina

Beilstein J. Org. Chem. 2023, 19, 778–788, doi:10.3762/bjoc.19.58

• of the methanol molecule occurs only for intermediate A and is not observed for product 11. It is important to emphasize that earlier, when discussing the mechanisms of the 6π-electrocyclization of various terarylenes accompanied by subsequent elimination of small molecules, we assumed a [1,9]-H

Bromination of endo-7-norbornene derivatives revisited: failure of a computational NMR method in elucidating the configuration of an organic structure

• Demet Demirci Gültekin,
• Arif Daştan,
• Yavuz Taşkesenligil,
• Cavit Kazaz,
• Yunus Zorlu and
• Metin Balci

Beilstein J. Org. Chem. 2023, 19, 764–770, doi:10.3762/bjoc.19.56

• have developed a machine learning-augmented DFT method for computational NMR, DU8ML, for fast and ‘accurate’ computational approaches [2]. They applied this computational method to a number of previously published organic compounds and claimed to have revised some structures and proposed new mechanisms