Total syntheses of highly oxidative Ryania diterpenoids facilitated by innovations in synthetic strategies

• Zhi-Qi Cao,
• Jin-Bao Qiao and
• Yu-Ming Zhao

Beilstein J. Org. Chem. 2025, 21, 2553–2570, doi:10.3762/bjoc.21.198

• . This field serves not only as a vital tool for molecular structure validation and the discovery of new reaction mechanisms but also as a fundamental driving force behind advances in related disciplines such as pharmaceutical science. Throughout this endeavor, innovations in methods and strategies

Catalytic enantioselective synthesis of selenium-containing atropisomers via C–Se bond formations

• Qi-Sen Gao,
• Zheng-Wei Wei and
• Zhi-Min Chen

Beilstein J. Org. Chem. 2025, 21, 2447–2455, doi:10.3762/bjoc.21.186

• phenyl-substituted benzoisoquinoline derivatives. Two plausible reaction mechanisms were proposed in the study: one involving oxidative addition of Int 4, a five-membered rhodium cyclic intermediate, followed by reductive elimination and the other proceeding via a bimolecular nucleophilic substitution

Recent advances in Norrish–Yang cyclization and dicarbonyl photoredox reactions for natural product synthesis

• Peng-Xi Luo,
• Jin-Xuan Yang,
• Shao-Min Fu and
• Bo Liu

Beilstein J. Org. Chem. 2025, 21, 2315–2333, doi:10.3762/bjoc.21.177

• review, drawing on examples from recently reported natural product syntheses, elaborates on reaction mechanisms, factors governing regioselectivity and stereoselectivity, and the impact of substrate structures on reaction pathways. These reactions not only serve as robust tools for the streamlined

Electrochemical cyclization of alkynes to construct five-membered nitrogen-heterocyclic rings

• Lifen Peng,
• Ting Wang,
• Zhiwen Yuan,
• Bin Li,
• Zilong Tang,
• Xirong Liu,
• Hui Li,
• Guofang Jiang,
• Chunling Zeng,
• Henry N. C. Wong and
• Xiao-Shui Peng

Beilstein J. Org. Chem. 2025, 21, 2173–2201, doi:10.3762/bjoc.21.166

• reaction mechanisms are disclosed if available. Keywords: alkyne; catalysis; cyclization; electrochemistry; five-membered ring; Introduction Organic five-membered rings, an essential class of organic compounds, not only are frequently used as important starting materials, intermediates or ligands in

Understanding the origin of stereoselectivity in the photochemical denitrogenation of 2,3-diazabicyclo[2.2.1]heptene and its derivatives with non-adiabatic molecular dynamics

• Leticia A. Gomes and
• Steven A. Lopez

Beilstein J. Org. Chem. 2025, 21, 2007–2020, doi:10.3762/bjoc.21.156

• light source. Electronic transitions to these excited states are impossible in the experiment and thus will not be considered for this photochemical mechanistic study. DBH photodenitrogenation mechanism We then turned our attention to the photochemical reaction mechanisms leading to the formation of

Measuring the stereogenic remoteness in non-central chirality: a stereocontrol connectivity index for asymmetric reactions

• Ivan Keng Wee On,
• Yu Kun Choo,
• Sambhav Baid and
• Ye Zhu

Beilstein J. Org. Chem. 2025, 21, 1995–2006, doi:10.3762/bjoc.21.155

• reaction mechanisms. Particularly, the application to reactions that establish non-central chirality allows a numeric measurement of the stereogenic remoteness – an intrinsic property of non-central chirality reflected by the large values of the indices (i ≥ 3). We anticipate that application of the

Photochemical reduction of acylimidazolium salts

• Michael Jakob,
• Nick Bechler,
• Hassan Abdelwahab,
• Fabian Weber,
• Janos Wasternack,
• Leonardo Kleebauer,
• Jan P. Götze and
• Matthew N. Hopkinson

Beilstein J. Org. Chem. 2025, 21, 1973–1983, doi:10.3762/bjoc.21.153

• an O-benzoylated intermediate species also being obtained under some conditions. Supported by TD-DFT studies, plausible reaction mechanisms for both processes were proposed. Moreover, further investigations employing silicon-containing additives allowed for an increase in the reduction yield beyond

Chiral phosphoric acid-catalyzed asymmetric synthesis of helically chiral, planarly chiral and inherently chiral molecules

• Wei Liu and
• Xiaoyu Yang

Beilstein J. Org. Chem. 2025, 21, 1864–1889, doi:10.3762/bjoc.21.145

• reaction mechanisms and applications of the chiral products for selected examples. Review Helical chirality Helicenes are a group of rigid polycyclic aromatic compounds composed of ortho-fused aromatic (hetero)cyclic rings, with their helically twisted conformation enforced by steric hindrance between

Continuous-flow-enabled intensification in nitration processes: a review of technological developments and practical applications over the past decade

• Feng Zhou,
• Chuansong Duanmu,
• Yanxing Li,
• Jin Li,
• Haiqing Xu,
• Pan Wang and
• Kai Zhu

Beilstein J. Org. Chem. 2025, 21, 1678–1699, doi:10.3762/bjoc.21.132

• nitration reactions follow first-order reactions due to the excessive use of nitric acid, which essentially still adhere to second-order reaction mechanisms. In kinetics studies of conventional nitration systems, while these processes usually involve liquid–liquid heterogeneous systems, researchers often

Structural analysis of stereoselective galactose pyruvylation toward the synthesis of bacterial capsular polysaccharides

• Tsun-Yi Chiang,
• Mei-Huei Lin,
• Chun-Wei Chang,
• Jinq-Chyi Lee and
• Cheng-Chung Wang

Beilstein J. Org. Chem. 2025, 21, 1671–1677, doi:10.3762/bjoc.21.131

• reaction mechanisms. Through this project, we aimed to explore the practical applications of PS A1 while simultaneously enhancing our understanding of synthetic chemistry. This endeavor reflects our commitment to advancing chemical knowledge and contributing to ongoing research in the field. Next, in-depth

Recent advances in amidyl radical-mediated photocatalytic direct intermolecular hydrogen atom transfer

• Hao-Sen Wang,
• Lin Li,
• Xin Chen,
• Jian-Li Wu,
• Kai Sun,
• Xiao-Lan Chen,
• Ling-Bo Qu and
• Bing Yu

Beilstein J. Org. Chem. 2025, 21, 1306–1323, doi:10.3762/bjoc.21.100

• the research of direct functionalization via HAT processes and the development of green chemistry in photocatalysis, this review will focus on the generation of amidyl radicals and reaction mechanisms and highlight the photocatalyzed reaction characteristics. This review aims to provide researchers

Enhancing chemical synthesis planning: automated quantum mechanics-based regioselectivity prediction for C–H activation with directing groups

• Julius Seumer,
• Nicolai Ree and
• Jan H. Jensen

Beilstein J. Org. Chem. 2025, 21, 1171–1182, doi:10.3762/bjoc.21.94

• chemistry’s structural variability. Cao et al. [14] developed an automated workflow that predicts the regioselectivity of C–H activations using extensive DFT calculations on a HPC cluster using up to 600 nodes, each containing 16 Intel Xeon E5-2670 cores. They considered two possible reaction mechanisms, an

A multicomponent reaction-initiated synthesis of imidazopyridine-fused isoquinolinones

• Ashutosh Nath,
• John Mark Awad and
• Wei Zhang

Beilstein J. Org. Chem. 2025, 21, 1161–1169, doi:10.3762/bjoc.21.92

• thiophene to reduce the diene's reactivity or altering the electrophilicity of the dienophile. Based on the computational analysis of the transition states, reaction mechanisms for the IMDA and the dehydration re-aromatization process are proposed in Scheme 5. In the IMDA reaction for the preparation of

Recent advances in synthetic approaches for bioactive cinnamic acid derivatives

• Betty A. Kustiana,
• Galuh Widiyarti and
• Teni Ernawati

Beilstein J. Org. Chem. 2025, 21, 1031–1086, doi:10.3762/bjoc.21.85

• these derivatives, this study aims to offer direct synthetic guidance and important insights into the rational design of novel cinnamate molecules with promising potential as future drug candidates. The reaction mechanisms will be discussed briefly. 2 Carboxyl group functionalization 2.1 O/N-acylations

Recent advances in controllable/divergent synthesis

• Jilei Cao,
• Leiyang Bai and
• Xuefeng Jiang

Beilstein J. Org. Chem. 2025, 21, 890–914, doi:10.3762/bjoc.21.73

• substrates, both dicarbonylation and monocarbonylation processes occurred simultaneously with Cu(OAc)2, favoring the dicarbonylation process. In contrast, using CuBr(Me2S) the monocarbonylation process was favored. Possible reaction mechanisms: First, CO coordinates with copper salts to form (carbonyl)copper

Formaldehyde surrogates in multicomponent reactions

• Cecilia I. Attorresi,
• Javier A. Ramírez and
• Bernhard Westermann

Beilstein J. Org. Chem. 2025, 21, 564–595, doi:10.3762/bjoc.21.45

• medium or lead to the formation of the same final product as that achieved with formaldehyde, but through different reaction mechanisms. Due to the importance of this research, this review aims to summarize and analyze the significant efforts made in this regard in recent years. Major emphasis will be

Recent advances in electrochemical copper catalysis for modern organic synthesis

• Yemin Kim and
• Won Jun Jang

Beilstein J. Org. Chem. 2025, 21, 155–178, doi:10.3762/bjoc.21.9

• , and benzamide, however, no relevant competitive oxidation peak was observed with only Cu(OAc)2. These results indicate that Cu(II) intermediate 5 was generated. Based on the mechanistic studies, the authors suggested plausible reaction mechanisms (Figure 4). First, the Cu(II) catalyst coordinates with

Direct trifluoroethylation of carbonyl sulfoxonium ylides using hypervalent iodine compounds

• Radell Echemendía,
• Carlee A. Montgomery,
• Fabio Cuzzucoli,
• Antonio C. B. Burtoloso and
• Graham K. Murphy

Beilstein J. Org. Chem. 2024, 20, 3182–3190, doi:10.3762/bjoc.20.263

• -mediated and SN2 reaction mechanisms. Ultimately, the nudged elastic band climbing image (NEB-CI) method predicted the SN2 pathway to be favoured, and transition state optimization showed this to possess a Gibbs free energy of activation of 24.3 kcal/mol. This report shows the ease with which sulfoxonium

Advances in the use of metal-free tetrapyrrolic macrocycles as catalysts

• Mandeep K. Chahal

Beilstein J. Org. Chem. 2024, 20, 3085–3112, doi:10.3762/bjoc.20.257

Synthesis of fluoroalkenes and fluoroenynes via cross-coupling reactions using novel multihalogenated vinyl ethers

• Yukiko Karuo,
• Keita Hirata,
• Atsushi Tarui,
• Kazuyuki Sato,
• Kentaro Kawai and
• Masaaki Omote

Beilstein J. Org. Chem. 2024, 20, 2691–2703, doi:10.3762/bjoc.20.226

• , Suzuki–Miyaura and Sonogashira cross-coupling with 1 has a broad substrate scope and can be used to synthesize various fluoroalkenes 2 and fluoroenyne 3. We speculate that these reaction mechanisms were similar to general cross-coupling mechanisms [45][46]. Conclusion We used Suzuki–Miyaura and

Machine learning-guided strategies for reaction conditions design and optimization

• Lung-Yi Chen and
• Yi-Pei Li

Beilstein J. Org. Chem. 2024, 20, 2476–2492, doi:10.3762/bjoc.20.212

• extensive effort. This involves complex parameter optimization, meticulous validation against experimental data, and careful consideration of diverse reaction conditions and possible reaction mechanisms [28][29]. Although some studies employ transition-state (TS) theory to simulate activation energies and

• reaction mechanisms. These models are particularly valuable in areas where experimental data are sparse or challenging to obtain, thereby extending the range of ML applications in chemistry. Educating the next generation of chemists, engineers, and data scientists in both ML and chemical synthesis is

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

• the N1-pathway by a product ratio of 4.5:1, which supports a pathway producing the observed experimental N2-product ratios with greater than 80% yield. The N1-product was again found to be lower in energy by 4.4 kcal/mol than the N2-product. To further explore whether the reaction mechanisms followed

Oxidation of benzylic alcohols to carbonyls using N-heterocyclic stabilized λ³-iodanes

• Thomas J. Kuczmera,
• Pim Puylaert and
• Boris J. Nachtsheim

Beilstein J. Org. Chem. 2024, 20, 1677–1683, doi:10.3762/bjoc.20.149

• reagents offer a viable alternative to traditional aryl-λ5-iodane-based oxidants, although further studies are necessary to fully understand their reaction mechanisms. Experimental General procedure for oxidation of benzylic alcohols 1a (700 µmol, 201 mg, 1.40 equiv), benzylic alcohol (3, 500 µmol, 1.00

• ) in MeCN (2.5 mL), respectively, were stirred at 60 °C for 2.5 h and quenched with Me2S (1.40 mmol). Possible reaction mechanisms via the formation of a) a Cl(I) species and b) the formation of an alkoxyiodane IIb. Both are initialized by the activated iodane I-OH, which was observed as c) I-OMe

Divergent role of PIDA and PIFA in the AlX₃ (X = Cl, Br) halogenation of 2-naphthol: a mechanistic study

• Kevin A. Juárez-Ornelas,
• Manuel Solís-Hernández,
• Pedro Navarro-Santos,
• J. Oscar C. Jiménez-Halla and
• César R. Solorio-Alvarado

Beilstein J. Org. Chem. 2024, 20, 1580–1589, doi:10.3762/bjoc.20.141

• energy than our proposed species. The reaction mechanisms are described in detail in this work and were found to be in excellent agreement with the experimental yield. These initial results confirmed that our proposed mechanism was energetically favored and therefore more plausible compared to

• reactions, we explored different pathways of the reaction mechanisms for the ortho-halogenation using 2-naphthol as a model substrate (Scheme 2). In such a way, we found a reaction pathway that was energetically favored. Based on our successful procedure for chlorination, we also developed an efficient

Generation of alkyl and acyl radicals by visible-light photoredox catalysis: direct activation of C–O bonds in organic transformations

• Mithu Roy,
• Bitan Sardar,
• Itu Mallick and
• Dipankar Srimani

Beilstein J. Org. Chem. 2024, 20, 1348–1375, doi:10.3762/bjoc.20.119

• of novel synthetic strategies. It has expanded the scope of available synthetic methods and contributed to the synthesis of complex molecules with high efficiency and selectivity. Ongoing research in this field continues to explore new catalysts, photosensitizers, and reaction mechanisms to further