Z-Selective semihydrogenation of alkynes via Ni/Lewis acid synergistic catalyzed system using DMF as hydrogen source and solvent

• Lei Kang,
• Haifeng Gao and
• Luo Yang

Beilstein J. Org. Chem. 2026, 22, 1004–1012, doi:10.3762/bjoc.22.79

• groups (F, Cl, Br) remained intact under the reaction conditions without side reactions, fully demonstrating the good functional group tolerance and substrate generality of this catalytic system. We speculate that the relatively moderate isolated yields mainly originate from the thermal polymerization of

Synthesis of sterically shielded piperidine nitroxides via acid-catalyzed heterocyclization of β-aminoketone derivatives with ketones

• Mark M. Gulman,
• Yurii I. Glazachev and
• Sergey A. Dobrynin

Beilstein J. Org. Chem. 2026, 22, 948–954, doi:10.3762/bjoc.22.74

• (MRI) [4][5] and as spin probes for Overhauser MRI in vivo [6]. Piperidin-1-oxyls played a key role in the development and industrial implementation of controlled polymerization of vinyl monomers (nitroxide-mediated polymerization, NMP) [7]. The unique redox properties of these radicals underpin their

• nitroxide-mediated polymerization (NMP), because shielding with ethyl or bulkier alkyl groups decreases accessibility of the nitroxide moiety and improves the equilibrium parameters in the reversible trapping of alkyl radical of the growing polymer chain [11]. This shielding also alters the redox properties

Hydrogen production from formic acid catalyzed by NHC–Cu complexes

• Orlando Santoro and
• Catherine S. J. Cazin

Beilstein J. Org. Chem. 2026, 22, 620–627, doi:10.3762/bjoc.22.48

• formate products. Excess H2 can be generated by dehydrogenative coupling of those species in the presence of the copper catalyst. Indeed, metal hydride systems have shown high catalytic activity in such a reaction [59][60]. In addition, the formation of products compatible with the polymerization of

Recent advances in the cleavage of non-activated amides

• Eun-Sol Choi and
• Hyo-Jun Lee

Beilstein J. Org. Chem. 2026, 22, 352–369, doi:10.3762/bjoc.22.23

• (Scheme 22c). Leveraging this LiHMDS-mediated transamidation strategy, Sumerlin et al. subsequently demonstrated efficient post-polymerization modification of acrylamide-based polymers 178 via direct transamidation (Scheme 22d) [74]. Installation of activating unit For the efficient transformation of

Spirobarbiturates with a pyrrolizidine moiety: synthesis, structure and biological evaluation

• Arthur A. Puzyrkov,
• Andrew S. Drachuk,
• Ekaterina A. Popova,
• Alexander V. Stepakov and
• Vitali M. Boitsov

Beilstein J. Org. Chem. 2026, 22, 274–288, doi:10.3762/bjoc.22.20

• such way that the barbituric moiety is directed to Trp 339, while the aryl substituent of the imide moiety is directed to Lys 212. This result agrees with the data on changes in the actin cytoskeleton and can be caused by a balance disturbance in the processes of actin polymerization and

Synthesis of diaryl phosphates using phytic acid as a phosphorus source

• Kazuya Asao,
• Seika Matsumoto,
• Haruka Mori,
• Riku Yoshimura,
• Takeshi Sasaki,
• Naoya Hirata,
• Yasuyuki Hayakawa and
• Shin-ichi Kawaguchi

Beilstein J. Org. Chem. 2026, 22, 213–223, doi:10.3762/bjoc.22.15

• -opening polymerization of some lactones [26][27] and are important for the syntheses of ionic liquids [28][29] and asymmetric phosphate esters. Furthermore, a novel metal extractant based on diaryl phosphate has recently been reported [30][31]. Phosphate esters are generally synthesized from phosphoryl

Synthesis and applications of alkenyl chlorides (vinyl chlorides): a review

• Daniel S. Müller

Beilstein J. Org. Chem. 2026, 22, 1–63, doi:10.3762/bjoc.22.1

• significantly influenced the overall yield. The decline in yield over time can potentially be attributed to polymerization side reactions of product 9 under the reaction conditions. Visual evidence of polymerization included difficulty in cleaning the reaction flask and the formation of solid polymer deposits

Sustainable electrochemical synthesis of aliphatic nitro-NNO-azoxy compounds employing ammonium dinitramide and their in vitro evaluation as potential nitric oxide donors and fungicides

• Alexander S. Budnikov,
• Nikita E. Leonov,
• Michael S. Klenov,
• Andrey A. Kulikov,
• Igor B. Krylov,
• Timofey A. Kudryashev,
• Aleksandr M. Churakov,
• Alexander O. Terent’ev and
• Vladimir A. Tartakovsky

Beilstein J. Org. Chem. 2025, 21, 2739–2754, doi:10.3762/bjoc.21.211

• applications in organic synthesis as precursors for free radicals in selective transformations [5][6][7][8][9][10][11] and polymerization initiators [12], energetic materials [13][14][15], NO donors [16][17], and organic light-emitting diodes (OLEDs) [18]. Despite the wide diversity of their applications

Tandem hydrothiocyanation/cyclization of CF₃-iminopropargyl alcohols with NaSCN in the presence of AcOH

• Ruslan S. Shulgin,
• Ol’ga G. Volostnykh,
• Anton V. Stepanov,
• Igor’ A. Ushakov,
• Alexander V. Vashchenko and
• Olesya A. Shemyakina

Beilstein J. Org. Chem. 2025, 21, 2694–2702, doi:10.3762/bjoc.21.207

• polymerization side reactions (Table 1, entries 16 and 17). As can be seen from Table 1, the use of strong acids reduces the yields of products due to side processes, whereas more polar solvents increase them. Finally, screening of thiocyanate salts showed that NaSCN was the most suitable source of HSCN for this

• alcohols with aromatic substituents 1d (R1 = Ph, R2 = Me) and 1e (R1 = R2 = Ph) were found to be less productive: the reaction required a 2-fold longer time (30 min) and resulted in lower yields of salts 2d,e likely due to side polymerization (Table 2, entries 3 and 4). At the same time, the yields of

C2 to C6 biobased carbonyl platforms for fine chemistry

• Jingjing Jiang,
• Muhammad Noman Haider Tariq,
• Florence Popowycz,
• Yanlong Gu and
• Yves Queneau

Beilstein J. Org. Chem. 2025, 21, 2103–2172, doi:10.3762/bjoc.21.165

• . Polylactic acid (PLA) and polyglycolic acid (PGA) are most important examples of biopolymers exhibiting interesting biodegradability properties [41]. The co-polymerization of PLA with glycolic acid was reported by Ayyoob and Kim [42]. High molecular weight poly-lactic-co-glycolic acid (PLGA) was obtained by

• the direct condensation and co-polymerization of both monomers promoted by a bicatalytic system including stannous chloride (SnCl2·2H2O) and methane sulfonic acid (MSA). PLGA films were prepared by the solvent casting technique, for which the presence of glycolic acid was found to increase their

• ). The obtained hydrocarbons exhibited higher density (0.78–0.88 g/cm3) and higher net heat of combustion (44.0–46.0 MJ/kg) than some commonly commercial fuels [194]. Multicomponent reactions involving the reactivity of furfural are also noteworthy. A Ugi four-component polymerization was developed to

Solar thermal fuels: azobenzene as a cyclic photon–heat transduction platform

• Jie Yan,
• Shaodong Sun,
• Minghao Wang and
• Si Wu

Beilstein J. Org. Chem. 2025, 21, 2036–2047, doi:10.3762/bjoc.21.159

• [47], where the azobenzene moieties undergo reversible photoisomerization and thermally induced reverse isomerization, enabling "energy charging–discharging" cycles (Figure 4a). Under ultraviolet (UV) irradiation (254 nm), the closely packed diacetylene polymers undergo polymerization to form π

Research progress on calixarene/pillararene-based controlled drug release systems

• Liu-Huan Yi,
• Jian Qin,
• Si-Ran Lu,
• Liu-Pan Yang,
• Li-Li Wang and
• Huan Yao

Beilstein J. Org. Chem. 2025, 21, 1757–1785, doi:10.3762/bjoc.21.139

• supramolecular polymers. Introducing α-CD onto DiCh effectively adjusts the flexibility of the spacer group, which in turn enhances supramolecular polymerization. Despite DiCh being captured by both α-CD and bisSC4A, the resultant assembly retains enzyme responsiveness, attributed to the dynamic equilibrium

Advances in nitrogen-containing helicenes: synthesis, chiroptical properties, and optoelectronic applications

• Meng Qiu,
• Jing Du,
• Nai-Te Yao,
• Xin-Yue Wang and
• Han-Yuan Gong

Beilstein J. Org. Chem. 2025, 21, 1422–1453, doi:10.3762/bjoc.21.106

• thia-bridged triarylamine[4]helicene-functionalized polynorbornenes 63a–c via ring-opening metathesis polymerization (ROMP), introducing helicene chirality into polymer backbones with tunable electrochromic behavior [78]. These polymers exhibit reversible pH-responsive color changes. For instance, 63a

Selective monoformylation of naphthalene-fused propellanes for methylene-alternating copolymers

• Kenichi Kato,
• Tatsuki Hiroi,
• Seina Okada,
• Shunsuke Ohtani and
• Tomoki Ogoshi

Beilstein J. Org. Chem. 2025, 21, 1183–1191, doi:10.3762/bjoc.21.95

• N2 adsorption and desorption. Molecular design for uniform microporosity and efficient polymerization is a next challenge. Conclusion In this work, we developed formylation on a naphthalene ring in [3.3.3]- and [4.3.3]-type fully π-fused propellanes. High selectivity was achieved for monoformylation

• -branched linear polymers, macrocyclic compounds, and molecular assemblies that incorporate propellanes as key 3D components. As a proof of concept, the formylated products were reduced to the corresponding alcohols and polymerized in acidic conditions. Although the degrees of polymerization were not high

Biobased carbon dots as photoreductants – an investigation by using triarylsulfonium salts

• Valentina Benazzi,
• Arianna Bini,
• Ilaria Bertuol,
• Mariangela Novello,
• Federica Baldi,
• Matteo Hoch,
• Alvise Perosa and
• Stefano Protti

Beilstein J. Org. Chem. 2025, 21, 1024–1030, doi:10.3762/bjoc.21.84

• photoreductants, and we considered triarylsulfonium salts Ar3S+X− as suitable probes. Such derivatives are photoreactive molecules characterized by a positively charged sulfur atom bonded to three aromatic moieties [20][21][22][23], mainly employed as photoacid generators in cationic polymerization [19]. Apart

On the photoluminescence in triarylmethyl-centered mono-, di-, and multiradicals

• Daniel Straub,
• Markus Gross,
• Mona E. Arnold,
• Julia Zolg and
• Alexander J. C. Kuehne

Beilstein J. Org. Chem. 2025, 21, 964–998, doi:10.3762/bjoc.21.80

Study of tribenzo[b,d,f]azepine as donor in D–A photocatalysts

• Katy Medrano-Uribe,
• Jorge Humbrías-Martín and
• Luca Dell’Amico

Beilstein J. Org. Chem. 2025, 21, 935–944, doi:10.3762/bjoc.21.76

• computational study to design new PCs to be employed in atom transfer radical polymerization (O-ATRP) [17]. Notably, the sulfur-based structure 2 showed excellent performance for this transformation. One year later, the same research group reported its use in a reversible addition-fragmentation chain-transfer

• (RAFT) polymerization [18]. Moreover, in 2022, Zysman-Colman and collaborators showed that molecule 3, initially synthesized as a TADF (thermally activated delayed fluorescence) emitter [14], can be used as a PC under electron-transfer (ET) and energy-transfer (EnT) processes (Figure 1a) [19]. All the

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

• difficult to separate [86][87][88]. Probably, the high reactivity of the imines generated by formaldehyde leads to their polymerization [84] or even to the incorporation of other nucleophiles present in the reaction mixture, such as the solvent or a second molecule of the amidine component (Scheme 32) [84

Unprecedented visible light-initiated topochemical [2 + 2] cycloaddition in a functionalized bimane dye

• Metodej Dvoracek,
• Brendan Twamley,
• Mathias O. Senge and
• Mikhail A. Filatov

Beilstein J. Org. Chem. 2025, 21, 500–509, doi:10.3762/bjoc.21.37

• promising strategy for synthesizing substituted cyclobutanes without the need for ultraviolet irradiation. Keywords: bimane; [2 + 2] cycloaddition; fluorescence; topochemical polymerization; X-ray crystallography; Introduction Topochemical polymerizations refer to polymerization reactions occurring in the

• primarily focused on [2 + 2] photocycloaddition in the solid state, making it one of the earliest known examples of topochemical polymerization and a valuable method for synthesizing substituted cyclobutanes [5]. These solid-state reactions are highly influenced by the arrangement of monomers within the

Red light excitation: illuminating photocatalysis in a new spectrum

• Lucas Fortier,
• Corentin Lefebvre and
• Norbert Hoffmann

Beilstein J. Org. Chem. 2025, 21, 296–326, doi:10.3762/bjoc.21.22

• states. In this section, the document highlights applications of these complexes in reactions like ring-closing metathesis and polymerization, where red light’s deeper penetration enhances yields and efficiency, particularly for large-scale reactions. The second section broadens the focus to explore

• the ruthenium(I) complex 2. In this study, T. Rovis et al. demonstrated a third advantage of working with red light: its penetrating power. To this end, a polymerization reaction of dicyclopentadiene 4 was investigated through various materials such as amber glass, white paper, a solution of

• hemoglobin, and silicon by selectively irradiating a specific area of the reaction medium with red light (660 nm) or blue light (456 nm), respectively (Scheme 2). The authors have demonstrated that this polymerization reaction proceeded much more efficiently under red light irradiation. Indeed, red light can

Three-component reactions of conjugated dienes, CH acids and formaldehyde under diffusion mixing conditions

• Dmitry E. Shybanov,
• Maxim E. Kukushkin,
• Eugene V. Babaev,
• Nikolai V. Zyk and
• Elena K. Beloglazkina

Beilstein J. Org. Chem. 2025, 21, 262–269, doi:10.3762/bjoc.21.18

• [4][5][6] and polymerization processes of unstable methylidene adducts [7][8][9], instead of the desired formation of a monocrotonic product. Therefore, heating [6][10][11][12][13][14] or Lewis acid activation [15][16][17][18] have often been used in the literature for successful multicomponent

• , which should significantly reduce undesirable polycondensations involving CH2O as well as polymerization of the intermediately formed methylidene derivatives. In this work, we generated methylidene adducts by formaldehyde condensation under diffusion mixing conditions in three-component reactions with

Hydrogen-bonded macrocycle-mediated dimerization for orthogonal supramolecular polymerization

• Wentao Yu,
• Zhiyao Yang,
• Chengkan Yu,
• Xiaowei Li and
• Lihua Yuan

Beilstein J. Org. Chem. 2025, 21, 179–188, doi:10.3762/bjoc.21.10

• cooperative intermolecular forces. Zinc ion-induced coordination with the macrocycle and a terpyridinium derivative enabled orthogonal polymerization, as revealed by 1H NMR, DLS, and TEM techniques. In addition, viscosity measurements showed a transition from oligomers to polymers at the critical

• polymerization concentration of 17 μM. These polymers were highly concentration-dependent. Establishing this new dimerization motif with shape-persistent H-bonded macrocycles widens the scope of noncovalent building blocks for supramolecular polymers and augurs well for the future development of functional

• photoluminescent materials [16]. In this regard, macrocycles emerged a decade ago as a “sticking” end for homo- and heterodifunctional monomers, enabling supramolecular polymerization [17]. So far, macrocycles that are applied to orthogonal self-assembly have been limited to three-dimensional rings, such as

Hot shape transformation: the role of PSar dehydration in stomatocyte morphogenesis

• Remi Peters,
• Levy A. Charleston,
• Karinan van Eck,
• Teun van Berlo and
• Daniela A. Wilson

Beilstein J. Org. Chem. 2025, 21, 47–54, doi:10.3762/bjoc.21.5

• ring-opening polymerization of N-carboxyanhydrides (NCAs), following a protocol adapted from Tian et al. [28]. High-purity monomers were obtained using this method, ensuring the subsequentially polymer synthesis proceeded with minimal impurities. Sequential polymerization commenced with poly(benzyl

• glutamate) (PBLG) as the hydrophobic block, which was done to prevent ending on a primary amine in the final product which could disrupt self-assembly due to its ionizable nature. Subsequently, PBLG served as a macroinitiator for the polymerization of sarcosine NCA, yielding the final polymer with high

• the vesicles at higher temperatures. d–f) Vesicles after shape transformation: illustrated at 60 °C, 70 °C, and 80 °C, respectively. i) Synthesis of benzyl glutamate NCA using phosgene and propylene oxide as a scavenger. ii) Ring-opening polymerization of BnGluNCA using benzylamine as initiator. iii

Emerging trends in the optimization of organic synthesis through high-throughput tools and machine learning

• Pablo Quijano Velasco,
• Kedar Hippalgaonkar and
• Balamurugan Ramalingam

Beilstein J. Org. Chem. 2025, 21, 10–38, doi:10.3762/bjoc.21.3

Cyclodextrin-based rotaxanes for polymer materials: challenge on simultaneous realization of inexpensive production and defined structures

• Yosuke Akae

Beilstein J. Org. Chem. 2024, 20, 3026–3049, doi:10.3762/bjoc.20.252

• comonomers (Scheme 4D) [67]. In this polyaddition reaction, various combinations of comonomers, e.g., di-isocyanate macro comonomers, bulky comonomers, or bulky diamine comonomers, enabled the fine-tuning of the resulting polymer properties. In addition to one-shot polymerization, chain extension and the

• , [3]rotaxane diol 10 was used as the initiator of the controlled ring-opening polymerization (ROP) of ε-caprolactone in the presence of a diphenyl phosphate catalyst to introduce the polyester main chain into the rotaxane framework; the successive end-capping reactions yielded macromolecular [3

• units are easily modified by acylation, the hydrophilicity of the rotaxane crosslinker (RC) could be tuned in this manner. This [3]rotaxane crosslinker RC was added 0.5 mol % on the standard free radical polymerization of vinyl monomers to afford rotaxane-crosslinked polymer (RCP) (Figure 15B). Similar