Visible-light-driven NHC and organophotoredox dual catalysis for the synthesis of carbonyl compounds

• Vasudevan Dhayalan

Beilstein J. Org. Chem. 2025, 21, 2584–2603, doi:10.3762/bjoc.21.200

• in biological and materials sciences (Scheme 8) [58]. In 2025, Xuan and colleagues, for the first time, developed a visible-light-driven dual catalytic method enabling the three-component borylacylation of substituted olefins 21. This novel strategy allows the rapid and efficient preparation of boryl

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

• hydroselenation of alkynes can provide an efficient and direct method for the synthesis of chiral vinyl selenides. However, to date, the enantioselective hydroselenation of alkynes remains underexplored. Building upon recent advances in rhodium-catalyzed asymmetric hydroselenation of olefins, in 2024, Li and co

Transformation of the cyclohexane ring to the cyclopentane fragment of biologically active compounds

• Natalya Akhmetdinova,
• Ilgiz Biktagirov and
• Liliya Kh. Faizullina

Beilstein J. Org. Chem. 2025, 21, 2416–2446, doi:10.3762/bjoc.21.185

• unseparated mixture of abeolupanes 245 and 246, in a ratio of 1.5–3:1, with a total yield of 89%. The interaction of compound 243 with BF3·Et2O in benzene at 70 °C gave a mixture of olefins 245 and 246 in a 1:2 ratio, with an overall yield of 88%. Similar transformations were carried out with methyl

• dihydrobetulinate 247. In the presence of montmorillonite K10, a ring contraction was observed to form an unseparated mixture of olefins 248 and 249 at a ratio

Enantioselective radical chemistry: a bright future ahead

• Anna C. Renner,
• Sagar S. Thorat,
• Hariharaputhiran Subramanian and
• Mukund P. Sibi

Beilstein J. Org. Chem. 2025, 21, 2283–2296, doi:10.3762/bjoc.21.174

• , initial examples of catalytic methodologies were based on chiral Lewis acid catalysis, with catalysts used in stoichiometric or sub-stoichiometric amounts [38][39]. Porter and Sibi disclosed the first enantioselective examples of conjugate additions to electron-deficient olefins by nucleophilic radicals

• transformations [43][44][45][46][47][48]. Using SOMO catalysis, MacMillan and co-workers developed a method for the synthesis of substituted pyrrolidines from β-aminoaldehydes and olefins in a formal [3 + 2] cycloaddition (Scheme 2) [44]. The transformation was proposed to proceed via a radical–polar crossover

• polycyclic products in a highly diastereo- and enantioselective manner [45]. The polyene substrates were designed to facilitate a radical cyclization process, with alternating electron-poor and electron-rich olefins so as to enable polarity matching of the olefins and radical intermediates. With this design

A chiral LC–MS strategy for stereochemical assignment of natural products sharing a 3-methylpent-4-en-2-ol moiety in their terminal structures

• Rei Suo,
• Raku Irie,
• Hinako Nakayama,
• Yuta Ishimaru,
• Yuya Akama,
• Masato Oikawa and
• Shiro Itoi

Beilstein J. Org. Chem. 2025, 21, 2243–2249, doi:10.3762/bjoc.21.171

• methods. We had also independently re-isolated compound 1 (1.2 mg) from the fungus Fusarium sp. (see Supporting Information File 1) and subsequently subjected 100 μg of 1 to the sequential degradation steps; (1) p-nitrobenzoylation of the two hydroxy groups, (2) RuO4 oxidation to cleave olefins including

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

The application of desymmetric enantioselective reduction of cyclic 1,3-dicarbonyl compounds in the total synthesis of terpenoid and alkaloid natural products

• Dong-Xing Tan and
• Fu-She Han

Beilstein J. Org. Chem. 2025, 21, 2085–2102, doi:10.3762/bjoc.21.164

• 69 and lactone 70 at 456 nm with fac-Ir(ppy)3 as the photocatalyst furnished a mixture of isomeric olefins. Finally, DBU-promoted the isomeric olefins conjugation and removal of the two silyl ether completed the first total synthesis of (+)-randainin D (13). Total synthesis of (−)-hunterine A and

Facile synthesis of hydantoin/1,2,4-oxadiazoline spiro-compounds via 1,3-dipolar cycloaddition of nitrile oxides to 5-iminohydantoins

• Juliana V. Petrova,
• Varvara T. Tkachenko,
• Victor A. Tafeenko,
• Anna S. Pestretsova,
• Vadim S. Pokrovsky,
• Maxim E. Kukushkin and
• Elena K. Beloglazkina

Beilstein J. Org. Chem. 2025, 21, 1552–1560, doi:10.3762/bjoc.21.118

• processes. It is worth noting that, in some cases, due to the high reactivity of nitrile oxides towards certain types of dipolarophiles, such as monosubstituted or activated by electron-acceptor groups olefins [31], no additional attention to this is required. However, when introducing obstructed

Wittig reaction of cyclobisbiphenylenecarbonyl

• Taito Moribe,
• Junichiro Hirano,
• Hideaki Takano,
• Hiroshi Shinokubo and
• Norihito Fukui

Beilstein J. Org. Chem. 2025, 21, 1454–1461, doi:10.3762/bjoc.21.107

• (Supporting Information File 1, Figures S22–S24). The decrease of CD intensity was fitted by a single exponential curve, affording half-lifes of 1.3 h for 1, 6.4 h for 3, and 29 h for 5. These results indicate that the transformation of carbonyl groups to exocyclic olefins is effective to retard racemization

• optical HOMO–LUMO gap of 5 despite the presence of 26 sp2 carbons is due to the cross-conjugation at the exocyclic olefins. Mono-olefin 3 is virtually non-emissive, similarly to CBBC 1, which could originate from the non-radiative decay via intersystem crossing due to the carbonyl group. In sharp contrast

Oxetanes: formation, reactivity and total syntheses of natural products

• Peter Gabko,
• Martin Kalník and
• Maroš Bella

Beilstein J. Org. Chem. 2025, 21, 1324–1373, doi:10.3762/bjoc.21.101

• ] Cycloadditions Another widely used method for oxetane synthesis is the [2 + 2] cycloaddition between carbonyls and olefins (Scheme 19), and the two main variations include light-induced Paternò–Büchi reactions and Lewis acid- or base-catalysed formal [2 + 2] cycloadditions. The main advantages of these reactions

• unprecedented Fe–Ni dual catalysis (Scheme 36) [86], which constitutes a more versatile alternative to Minisci or Friedel–Crafts alkylations. The reaction couples mono-, di- and trisubstituted olefins with (hetero)aryl halides, and it was used to prepare a relatively large library of 3-alkyl-3-(hetero

Recent advances in oxidative radical difunctionalization of N-arylacrylamides enabled by carbon radical reagents

• Jiangfei Chen,
• Yi-Lin Qu,
• Ming Yuan,
• Xiang-Mei Wu,
• Heng-Pei Jiang,
• Ying Fu and
• Shengrong Guo

Beilstein J. Org. Chem. 2025, 21, 1207–1271, doi:10.3762/bjoc.21.98

• yields (80f,g). Perfluoroalkyl iodides, ranging from trifluoromethyl to longer perfluorinated chains, also performed well (80h). However, substrates with unprotected N–H bonds (80i) and monosubstituted olefins (80j) exhibited limited reactivity. Mechanistic investigations suggested a radical-mediated

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

• /carbenoid reactions: α-Diazocarbonyl compounds are useful reagents especially to synthesize aziridine compounds through reactive carbene species. A few examples of utilizing α-diazocarbonyl compounds to prepare olefins have also been reported, either mediated by metal catalysts or through a more sustainable

• are cis-coplanar resulting in the Z-isomer product. 3.1.4 Metathesis reactions: Metathesis reactions are one of the most crucial approaches to preparing olefins. Grubbs and Grubbs–Hoveyda catalysts are among the most frequently used catalysts for the stereoselective construction of C=C bonds. Moreover

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

• , with particular attention to the 1,2-difunctionalization of olefins by alkyl halides via atom transfer radical addition processes in the presence of amorphous nitrogen-doped carbon dots (Scheme 1a) [20]. In the framework of this research topic, we decided to investigate the use of carbon dots as

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

• regulating the chemical selectivity of a three-component radical cascade reaction involving α-brominated aryl ketones 72, olefins 73, and 1-methylquinoxalin-2(1H)-one (74) with an inorganic base, they were able to obtain two important types of products with high yield and enantioselectivity. Through

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

• without requiring stoichiometric organometallic reagents [49] (Scheme 10). The distinctive reactivity of the CuH species allows for precise control over the stereochemical outcome through the regio- and enantioselective hydrocupration of olefins 27, followed by stereospecific trapping with allylic

• styrenes with diverse electronic properties as well as those containing sensitive functional groups such as esters, amides, and vinyl halides, to yield the desired β-chiral olefins in high enantioselectivity. Notably, the methodology could even be applied to vinylferrocene and vinylsilane derivatives

• inherent limitations with molecules possessing unsaturated functionalities due to competitive hydrocupration pathways. The approach using 1,1-diborylalkanes 47 circumvents these chemoselectivity issues and enables a selective allylic substitution of substrates containing olefins and alkynes with excellent

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

• topochemical reactions. Currently, topochemically active monomers are limited to large, planar aromatic molecules, aryl-substituted olefins, and polyenes, often complexed with metals. These compounds are frequently employed in the construction of metal-organic frameworks [13][14][15]. The limited range of

Organocatalytic kinetic resolution of 1,5-dicarbonyl compounds through a retro-Michael reaction

• James Guevara-Pulido,
• Fernando González-Pérez,
• José M. Andrés and
• Rafael Pedrosa

Beilstein J. Org. Chem. 2025, 21, 473–482, doi:10.3762/bjoc.21.34

• olefins with a wide range of nucleophiles, with many organocatalyzed asymmetric examples highlighted in the literature [23][24]. We have observed that the enantioenriched 1,5-dicarbonyl Michael adducts, synthesized via organocatalyzed reaction of cinnamaldehyde with benzyl phenyl ketone, undergo

Photomechanochemistry: harnessing mechanical forces to enhance photochemical reactions

• Francesco Mele,
• Ana M. Constantin,
• Andrea Porcheddu,
• Raimondo Maggi,
• Giovanni Maestri,
• Nicola Della Ca’ and
• Luca Capaldo

Beilstein J. Org. Chem. 2025, 21, 458–472, doi:10.3762/bjoc.21.33

• acylation of electrophilic olefins (Scheme 11C). Compared to solution-phase photocatalysis, photomechanochemical conditions allowed to reduce the reaction time from 24 h to 3 h while maintaining comparable yields. Finally, the authors proved that photomechanochemistry contributes to the initial rate

Visible-light-promoted radical cyclisation of unactivated alkenes in benzimidazoles: synthesis of difluoromethyl- and aryldifluoromethyl-substituted polycyclic imidazoles

• Yujun Pang,
• Jinglan Yan,
• Nawaf Al-Maharik,
• Qian Zhang,
• Zeguo Fang and
• Dong Li

Beilstein J. Org. Chem. 2025, 21, 234–241, doi:10.3762/bjoc.21.15

• . Furthermore, terminal olefins with varying chain lengths also reacted successfully, resulting in 5-membered and 7-membered cyclized products (3l–p) with yields between 44% and 66%. The lower yields in these cases might be due to the low reactivity of the intermediate C (Scheme 3), which may have made it less

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

• the enantioselective dicarbofunctionalization of olefins, using photoelectrocatalysis with asymmetric copper catalysis (Figure 8) [57]. This asymmetric heteroarylcyanation of arylalkenes 27 via C–H functionalization has a broad substrate scope, including various arylalkenes and heteroarenes, yielding

• intermediate 82 undergoes enantiodetermining reductive elimination to deliver the chiral phosphinoylcyanation products 81 and regenerate the Cu(I) species. The Lin group developed an electrochemical approach for the asymmetric hydrocyanation of olefins, facilitated by a Cu/Co dual electrocatalytic system

• enantioenriched nitrile products 89 and a reduced Cu(I) complex 94, which is reoxidized through anodic oxidation. The 1,2-diamine moiety is present in numerous natural products and bioactive compounds. In 2022, Xu et al. reported the Cu-catalyzed electrocatalytic diazidation of olefins with ppm-level catalyst

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

• ] cycloaddition reaction with the nitroalkene produces the pyrrolidine XXVII, which then aromatizes by extrusion of HNO2 (Scheme 21) [38]. Substituted pyrrolidines 30 were achieved in an enantioselective form starting from amino acid esters, electron-poor olefins and 4-substituted-2-picolinaldehydes or 4

Giese-type alkylation of dehydroalanine derivatives via silane-mediated alkyl bromide activation

• Perry van der Heide,
• Michele Retini,
• Fabiola Fanini,
• Giovanni Piersanti,
• Francesco Secci,
• Daniele Mazzarella,
• Timothy Noël and
• Alberto Luridiana

Beilstein J. Org. Chem. 2024, 20, 3274–3280, doi:10.3762/bjoc.20.271

• slight increase in chemical yield. Giese reaction: Radical addition on olefins with an electron-withdrawing group (EWG) followed by a HAT or SET and protonation; halogen-atom transfer: (a) tin-mediated XAT, (b) XAT initiated by a photocatalyst (PC) and mediated by boranes (B), silanes (Si) or alkylamines

Recent advances in transition-metal-free arylation reactions involving hypervalent iodine salts

• Ritu Mamgain,
• Kokila Sakthivel and
• Fateh V. Singh

Beilstein J. Org. Chem. 2024, 20, 2891–2920, doi:10.3762/bjoc.20.243

• olefins, showcasing an efficient utilization of aryliodonium salts in the process. Later in the same year, Song and colleagues reported a protocol for the efficient synthesis of 2-aryl-substituted quinolines 27 and pyridine N-oxides 29 [63]. This reaction involved the selective arylation at the C2

Synthesis of pyrrole-fused dibenzoxazepine/dibenzothiazepine/triazolobenzodiazepine derivatives via isocyanide-based multicomponent reactions

• Marzieh Norouzi,
• Mohammad Taghi Nazeri,
• Ahmad Shaabani and
• Behrouz Notash

Beilstein J. Org. Chem. 2024, 20, 2870–2882, doi:10.3762/bjoc.20.241

• .20.241 Abstract An efficient and facile synthesis of pyrrole-fused dibenzoxazepine/dibenzothiazepine/triazolobenzodiazepine derivatives was developed through the isocyanide-based multicomponent reaction of isocyanides, gem-diactivated olefins, and cyclic imines such as dibenzoxazepine, dibenzothiazepine

• addition to the application of isocyanides in a variety of MCRs, one of the unique reactions involves the formation of zwitterions from isocyanides upon reaction with acetylene and active olefin compounds such as alkyl acetylenedicarboxylates and gem-diactivated olefins. Due to having nucleophilic and

• ]. Here, we report an efficient and facile approach for the synthesis of pyrrole-fused dibenzoxazepine, dibenzothiazepine, and triazolobenzodiazepine derivatives via I-MCRs of gem-diactivated olefins, isocyanides, and cyclic imines (dibenzoxazepines, benzothiazepine, and triazolobenzodiazepine) under

A review of recent advances in electrochemical and photoelectrochemical late-stage functionalization classified by anodic oxidation, cathodic reduction, and paired electrolysis

• Nian Li,
• Ruzal Sitdikov,
• Ajit Prabhakar Kale,
• Joost Steverlynck,
• Bo Li and
• Magnus Rueping

Beilstein J. Org. Chem. 2024, 20, 2500–2566, doi:10.3762/bjoc.20.214