Recent advances in allylation of chiral secondary alkylcopper species

• Minjae Kim,
• Gwanggyun Kim,
• Doyoon Kim,
• Jun Hee Lee and
• Seung Hwan Cho

Beilstein J. Org. Chem. 2025, 21, 639–658, doi:10.3762/bjoc.21.51

• transmetalation of organolithium and organoboron compounds, copper hydride catalysis, and enantiotopic-group-selective transformations of 1,1-diborylalkanes. Detailed mechanistic insights into stereochemical control and current challenges in this field are also discussed. Keywords: allylic substitution; chiral

• generating configurationally unstable organocopper species with secondary carbon–metal bonds, their unique properties, and related mechanistic insights. This review also aims to outline future research directions and prospects, contributing to the development of more efficient and selective copper-catalyzed

Cu(OTf)₂-catalyzed multicomponent reactions

• Sara Colombo,
• Camilla Loro,
• Egle M. Beccalli,
• Gianluigi Broggini and
• Marta Papis

Beilstein J. Org. Chem. 2025, 21, 122–145, doi:10.3762/bjoc.21.7

• Venezian 21, 20133, Milano, Italy 10.3762/bjoc.21.7 Abstract This review reports the achievements in copper(II) triflate-catalyzed processes concerning the multicomponent reactions, applied to the synthesis of acyclic and cyclic compounds. In particular, for the heteropolycyclic systems mechanistic

• insights were outlined as well as cycloaddition and aza-Diels–Alder reactions were included. These strategies have gained attention due to their highly atom- and step-economy, one-step multi-bond forming, mild reaction conditions, low cost and easy handling. Keywords: cascade process; copper catalysis

Regioselective alkylation of a versatile indazole: Electrophile scope and mechanistic insights from density functional theory calculations

• Pengcheng Lu,
• Luis Juarez,
• Paul A. Wiget,
• Weihe Zhang,
• Krishnan Raman and
• Pravin L. Kotian

Beilstein J. Org. Chem. 2024, 20, 1940–1954, doi:10.3762/bjoc.20.170

Electrochemical radical cation aza-Wacker cyclizations

• Sota Adachi and
• Yohei Okada

Beilstein J. Org. Chem. 2024, 20, 1900–1905, doi:10.3762/bjoc.20.165

• tetrasubstituted alkene 14. Cyclic voltammetric studies have provided further mechanistic insights into electrochemical aza-Wacker cyclizations. As reported by Yoon, a trisubstituted alkene is oxidized at significantly lower potential than aryl sulfonamides, suggesting that the reactions were initiated by single

Tetrabutylammonium iodide-catalyzed oxidative α-azidation of β-ketocarbonyl compounds using sodium azide

• Christopher Mairhofer,
• David Naderer and
• Mario Waser

Beilstein J. Org. Chem. 2024, 20, 1510–1517, doi:10.3762/bjoc.20.135

• to previous reports [31][41][42][43], the herein reported protocol most likely proceeds via in situ formation of a catalytically competent quaternary ammonium hypoiodite species which then facilities the coupling of the two inherently nucleophilic reaction partners. To get further mechanistic

• insights we also carried out our standard reaction (Table 1, entry 14) in the presence of well-established radical traps like TEMPO, di-tert-butylhydroxytoluene (BHT), or 1,1-diphenylethene (DPE). In neither case any influence on the yield was observed, thus ruling out a mechanism involving radical species

Mechanistic investigations of polyaza[7]helicene in photoredox and energy transfer catalysis

• Johannes Rocker,
• Till J. B. Zähringer,
• Matthias Schmitz,
• Till Opatz and
• Christoph Kerzig

Beilstein J. Org. Chem. 2024, 20, 1236–1245, doi:10.3762/bjoc.20.106

• potentials of Aza-H and the substrates and initial steady-state fluorescence quenching experiments (Scheme 1, left), but detailed mechanistic insights and direct evidence of the transient radical ions could not be obtained yet [45]. Figure 1A illustrates the absorption and emission spectra of Aza-H in MeCN

• species in a three-component sulfonylation/arylation reaction, whereas the unexplored triplet state is responsible for the decomposition of the photocatalyst. Photoinduced radical cation formation and thermal regeneration could be unambiguously observed, providing deep mechanistic insights into the

Palladium-catalyzed three-component radical-polar crossover carboamination of 1,3-dienes or allenes with diazo esters and amines

• Geng-Xin Liu,
• Xiao-Ting Jie,
• Ge-Jun Niu,
• Li-Sheng Yang,
• Xing-Lin Li,
• Jian Luo and
• Wen-Hao Hu

Beilstein J. Org. Chem. 2024, 20, 661–671, doi:10.3762/bjoc.20.59

• modification of pharmaceutical scaffolds. Naturally, we were eager to acquire detailed mechanistic insights into this protocol. To validate the radical nature of this transformation, both model reactions of 1,3-diene 2a and allene 5a were terminated completely with 2.5 equiv 2,2,6,6-tetramethylpiperidinyloxyl

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

• . Mechanistic insights on the irreversible phase 2: first steps Once phase 1 was analyzed in detail, we studied the irreversible formation of C–C bonds in the interdimer region, known as phase 2 in the dimerization process. Due to the large number of possible pathways to be investigated, we made use of a

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

• -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

α-(Aminomethyl)acrylates as acceptors in radical–polar crossover 1,4-additions of dialkylzincs: insights into enolate formation and trapping

• Angel Palillero-Cisneros,
• Paola G. Gordillo-Guerra,
• Fernando García-Alvarez,
• Olivier Jackowski,
• Franck Ferreira,
• Fabrice Chemla,
• Joel L. Terán and
• Alejandro Perez-Luna

Beilstein J. Org. Chem. 2023, 19, 1443–1451, doi:10.3762/bjoc.19.103

• . Mechanistic insights The last part of our work was devoted to gain mechanistic insight for the developed reaction protocols through several diagnostic experiments. Regarding the 1,4-addition process, the lower reactivity noted in the absence of air (Table 2, entry 5) represents already a strong indication for

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

• TADF was observed. This is a solid experimental evidence that spin–vibronic coupling is essential for TADF, and the 3CS → 1CS rISC is slow, without the coupling with the intermediate 3LE state. The conventionally used transient luminescence spectral method is unable to supply such in-depth mechanistic

• insights into the TADF mechanism. For the dyads with the oxidized PTZ units, however, the CS state energy is increased by up to 0.8 eV, yet the 3LE state energy does not change. Thus the spin–vibronic coupling between the 3LE and 3CS is weak and no TADF was observed for this dyad only a long-lived 3LE

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

• summarized so that the chemists, researchers, and pharmaceutical industries find its effectiveness in near future for the synthesis of potent, novel, and non-toxic drug molecules. Keywords: functionalization; imidazole N-oxide; mechanistic insights; multicomponent reaction; nucleophilic substitution

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

• determined the stereoselectivity of the reaction arises from the unattractive interactions imposed from the sterically hindered endo-face of the bicyclic alkene. The mechanistic insights gained from this combined experimental and theoretical study will facilitate further future methodology development in

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

• step by chloride abstraction that leads to the formation of an oxocarbenium intermediate, which then undergoes the stereoselective addition of the nucleophile. Mechanistic insights revealed that two thiourea molecules are, in fact, needed and cooperatively participate in the activation of 73. However

Microwave-assisted multicomponent reactions in heterocyclic chemistry and mechanistic aspects

• Shivani Gulati,
• Stephy Elza John and
• Nagula Shankaraiah

Beilstein J. Org. Chem. 2021, 17, 819–865, doi:10.3762/bjoc.17.71

• -MCRs and their mechanistic insights over the past decade and shed light on its advantage over the conventional approach. Keywords: cycloaddition; Knoevenagel condensation; Michael addition; microwave; multicomponent reactions; Introduction Recently, organic chemists are focussed to develop

• single nitrogen-containing heterocycles. A mechanistic understanding of a reaction progression promotes better conceptualization of strategies effectively. This review aims at bridging the hiatus of the previous reviews with mechanistic insights into the MWA-MCRs employed for the synthesis of organic and

Synthesis and properties of oligonucleotides modified with an N-methylguanidine-bridged nucleic acid (GuNA[Me]) bearing adenine, guanine, or 5-methylcytosine nucleobases

• Naohiro Horie,
• Takao Yamaguchi,
• Shinji Kumagai and
• Satoshi Obika

Beilstein J. Org. Chem. 2021, 17, 622–629, doi:10.3762/bjoc.17.54

• expected to provide further mechanistic insights into how small substituents affect the efficacy and safety of therapeutic oligonucleotides. Thus, the synthesis of GuNA[Me] phosphoramidites bearing other typical nucleobases, i.e., adenine (A), guanine (G), or 5-methylcytosine (mC), instead of the

pH- and concentration-dependent supramolecular self-assembly of a naturally occurring octapeptide

• Goutam Ghosh and
• Gustavo Fernández

Beilstein J. Org. Chem. 2020, 16, 2017–2025, doi:10.3762/bjoc.16.168

• (Glu−) amino acids [73][74]. Mechanistic insights into the observed conformational transformation via molecular dynamics simulations are underway in our laboratory. Conclusion In summary, we synthesized a naturally occurring amphiphilic peptide fragment, PEP-1, from a β-sheet lectin protein, galectin-1

One-pot synthesis of isosorbide from cellulose or lignocellulosic biomass: a challenge?

• Isaline Bonnin,
• Raphaël Mereau,
• Thierry Tassaing and
• Karine De Oliveira Vigier

Beilstein J. Org. Chem. 2020, 16, 1713–1721, doi:10.3762/bjoc.16.143

• this reaction under continuous flow using two catalytic beds. Finally, we emphasize that mechanistic insights on the catalytic conversion of biomass-derived platform molecules are required to make this value chain competitive with respect to the traditional synthesis of chemicals from fossil fuels. In

Understanding the role of active site residues in CotB2 catalysis using a cluster model

• Keren Raz,
• Ronja Driller,
• Thomas Brück,
• Bernhard Loll and
• Dan T. Major

Beilstein J. Org. Chem. 2020, 16, 50–59, doi:10.3762/bjoc.16.7

• reactivity of the isolated species and provided crucial mechanistic insights, the biorelevant mechanism cannot be fully understood without taking into account the enzyme–solvent environment. A common problem when studying these enzymes is the lack of high-resolution crystal structures that are biologically

A novel three-component reaction between isocyanides, alcohols or thiols and elemental sulfur: a mild, catalyst-free approach towards O-thiocarbamates and dithiocarbamates

• András György Németh,
• György Miklós Keserű and
• Péter Ábrányi-Balogh

Beilstein J. Org. Chem. 2019, 15, 1523–1533, doi:10.3762/bjoc.15.155

• synthesis of an analogous compound was accomplished by Sayahi et al. starting from isothiocyanates in the presence of CuBr [106]. As aforementioned, in some cases only isothiocyanate 8 was detected and/or isolated. Thus, in order to gain mechanistic insights on the generation of 3a, we performed a series of

Steroid diversification by multicomponent reactions

• Leslie Reguera,
• Cecilia I. Attorresi,
• Javier A. Ramírez and
• Daniel G. Rivera

Beilstein J. Org. Chem. 2019, 15, 1236–1256, doi:10.3762/bjoc.15.121

• organocatalytic multicomponent approaches [32] not only the chiral steroidal isocyanide but also the bifunctional component 30, used in enantiomerically enriched form, plays a crucial role in the high stereoselection. The mechanistic insights of this class of MCR were disclosed in the original publication [31

Bioinspired cobalt cubanes with tunable redox potentials for photocatalytic water oxidation and CO₂ reduction

• Zhishan Luo,
• Yidong Hou,
• Jinshui Zhang,
• Sibo Wang and
• Xinchen Wang

Beilstein J. Org. Chem. 2018, 14, 2331–2339, doi:10.3762/bjoc.14.208

• catalysis, but also providing valuable structural information to understand the mechanistic insights of catalytic behavior [24][25][26][27]. In addition, the molecular catalysts can either be dissolved in liquids affording a homogeneous catalytic system [28][29], or immobilized on solid surfaces for

Thiocarbonyl-enabled ferrocene C–H nitrogenation by cobalt(III) catalysis: thermal and mechanochemical

• Santhivardhana Reddy Yetra,
• Zhigao Shen,
• Hui Wang and
• Lutz Ackermann

Beilstein J. Org. Chem. 2018, 14, 1546–1553, doi:10.3762/bjoc.14.131

• ) cobalt-catalyzed C–H amidations of thiocarbonylferrocenes by weak coordination, (ii) thermal and mechanochemical [98][99][100] cobalt-catalyzed ferrocene C–H nitrogenations, (iii) versatile access to synthetically useful aminoketones, and (iv) key mechanistic insights on facile C–H cobaltation. Results

Recent highlights in biosynthesis research using stable isotopes

• Jan Rinkel and
• Jeroen S. Dickschat

Beilstein J. Org. Chem. 2015, 11, 2493–2508, doi:10.3762/bjoc.11.271

• old-fashioned, but rather still yield important mechanistic insights in biosynthetic pathways that would otherwise never be obtained. Emphazising the same principle, feeding of even simpler precursors such as labeled acetate can give useful hints to carbon and hydrogen rearrangement, as shown for

Beyond catalyst deactivation: cross-metathesis involving olefins containing N-heteroaromatics

• Kevin Lafaye,
• Cyril Bosset,
• Lionel Nicolas,
• Amandine Guérinot and
• Janine Cossy

Beilstein J. Org. Chem. 2015, 11, 2223–2241, doi:10.3762/bjoc.11.241

• of N-heteroaromatics containing olefins in metathesis has been less documented. In this review, we would like to give an overview of successful metatheses involving alkenes that possess N-heteroaromatics in order to delineate some guidelines. Some mechanistic insights dealing with catalyst

• deactivation caused by amino derivatives will be first presented and discussed. RCM and CM involving alkenes possessing N-heteroaromatics will be then successively examined [38]. Review Mechanistic insights into amine-induced catalyst deactivation Recently, intensive studies dealing with ruthenium catalyst