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

• delivered 68. A one-pot desilylation/oxidation of 67 produced an aldehyde, which was subject to selective nucleophilic addition in the presence of a ketone, allowing for access to the furan precursor 68 [37]. Oxidation–cyclization–aromatization of 68 with Dess–Martin periodinane (DMP) constructed the

Pathway economy in cyclization of 1,n-enynes

• Hezhen Han,
• Wenjie Mao,
• Bin Lin,
• Maosheng Cheng,
• Lu Yang and
• Yongxiang Liu

Beilstein J. Org. Chem. 2025, 21, 2260–2282, doi:10.3762/bjoc.21.173

• . When the gold(I) complex [JohnPhosAu(CH3CN)SbF6] was employed, a subsequent 5-exo-dig cyclization followed by aromatization steps occurred, ultimately affording the 2-sulfonylmethylpyrrole 118 (Scheme 24, path a). Conversely, utilization of the Ph3PAuCl/AgSbF6 catalytic system induced a different

• intermediate 150. Subsequent aromatization and ring expansion afforded benzene derivatives 151 (Scheme 31, path a). Conversely, E-configured substrates underwent gold-catalyzed alkyne activation, triggering terminal alkene 5-exo-dig cyclization to form carbocationic intermediate 152. Alcohols nucleophilically

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

• bicyclic alkanes, used as fuel additives, by hydrodeoxygenation catalyzed by iridium/rhenium oxide supported on silica [182]. Conversion of furfural to amines: The synthesis of m-xylylenediamine from furfural and acrylonitrile through a Diels–Alder/aromatization sequence was developed by Wischet and Jérôme

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

• rings, followed by dehydration to afford pentacyclic product 125. Finally, a five-step operation including the 1,2-addition of 125 with iPrLi, PCC oxidation of the resulting tertiary alcohol, oxidative aromatization and in situ neutralization/oxidation, acid-mediated 1,6-addition with H2O, and

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

• aromatization process, in 2023 our group reported the asymmetric synthesis of various azahelicenes 8 from polycyclic arylamines 5, dienamides 6 and aldehydes 7 (Scheme 2) [13]. This methodology demonstrates a broad substrate scope, enabling the efficient asymmetric synthesis of diverse aza[5]helicenes 8a–d and

• dehydrogenation. Almost simultaneously, the Li group independently reported the asymmetric synthesis of chiral quinohelicenes using a similar sequential asymmetric Povarov reaction and oxidative aromatization strategy [14]. In their study, they employed 3-vinylindoles 10 in the CPA-catalyzed asymmetric Povarov

• reaction with polycyclic arylamines 9 and various aromatic aldehydes 11, resulting in a range of quinoline-containing azahelicenes 12 with moderate yield and excellent enantioselectivity after DDQ-mediated oxidative aromatization (Scheme 3). Notably, they not only expanded the substrate scope to encompass

Fe-catalyzed efficient synthesis of 2,4- and 4-substituted quinolines via C(sp²)–C(sp²) bond scission of styrenes

• Prafull A. Jagtap,
• Manish M. Petkar,
• Vaishnavi R. Sawant and
• Bhalchandra M. Bhanage

Beilstein J. Org. Chem. 2025, 21, 1799–1807, doi:10.3762/bjoc.21.142

• formation of intermediates III and III′. Subsequent electrophilic cyclization/C–H annulation of the aromatic amine, followed by aromatization, afford intermediates V and V′. The oxidative dehydrogenation of intermediates V and V′ then results in the formation of products 3a and 3a′ and the regeneration of

Catalytic asymmetric reactions of isocyanides for constructing non-central chirality

• Jia-Yu Liao

Beilstein J. Org. Chem. 2025, 21, 1648–1660, doi:10.3762/bjoc.21.129

• lactones with carbon nucleophiles. The success lies in the tandem enantioselective ring-opening of lactones with α-acidic isocyanides, followed by a rapid cyclization driven by aromatization, overcoming the long-standing stereochemical leakage problem caused by the undesired lactol formation [45

• with both axial and central chirality, followed by 2) ring-strain and aromatization-driven elimination, which elucidating the observed unusual torsional strain-independent reactivity. In addition, products bearing a tert-butyl ester group were smoothly converted into structurally novel axially chiral

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

• , enantioselective synthetic approach toward azahelicenes via a chiral phosphoric acid-catalyzed multicomponent Povarov reaction or oxidative aromatization [32]. Among the synthesized compounds, compound 19 displayed dual absorption bands at 260 and 325 nm and emission peaks at 420 and 440 nm, which red-shifted to

High-pressure activation for the solvent- and catalyst-free syntheses of heterocycles, pharmaceuticals and esters

• Kelsey Plasse,
• Valerie Wright,
• Guoshu Xie,
• R. Bernadett Vlocskó,
• Alexander Lazarev and
• Béla Török

Beilstein J. Org. Chem. 2025, 21, 1374–1387, doi:10.3762/bjoc.21.102

• the water that forms as a by-product during the cyclization–aromatization sequence. The gas chromatograms of the three crude products appeared essentially 100% pure, neither starting material nor other by-products were observed. In order to explain the outcome of the above reactions, the reaction

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

• radical anion 15 was reduced by the photocatalyst Ir(Fppy)3 from the reagent 11. The resulting anion 14 underwent aromatization to release a nitrile anion, subsequently yielding product 12. This strategy also successfully produced products 16 and 17 with yields of 85% and 56%, respectively, from

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

• intermediate 12. Subsequent intramolecular cyclization and oxidative aromatization lead to the final isoxazoline-featured oxindole 9. In 2017, Li’s group reported an oxidative divergent bicyclization of 1,n-enynes through α-C(sp3)–H functionalization of alkyl nitriles using a Sc(OTf)3 and Ag2O system (Scheme 7

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

• (IMDA), and dehydrative re-aromatization reactions for the synthesis of imidazopyridine-fused isoquinolinones is developed. Gaussian computation analysis on the effect of the substitution groups for the IMDA reaction is performed to understand the reaction mechanism. Keywords: Groebke–Blackburn

• –Bienaymé (GBB); imidazopyridine; intramolecular Diels–Alder (IMDA); isoquinolinone; multicomponent reaction (MCR); re-aromatization; Introduction Multicomponent reactions (MCRs) have intrinsic green chemistry advantages of synthetic efficiency and operational simplicity. Performing post-condensational

• compounds [18]. Presented in this paper is a new synthetic route involving GBB, N-acylation and IMDA reactions for making intermediate III followed by dehydrative re-aromatization to give imidazopyridine-fused isoquinolinones C (Scheme 1C). Results and Discussion Following the reported procedures [10], the

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

Studies on the syntheses of β-carboline alkaloids brevicarine and brevicolline

• Benedek Batizi,
• Patrik Pollák,
• András Dancsó,
• Péter Keglevich,
• Gyula Simig,
• Balázs Volk and
• Mátyás Milen

Beilstein J. Org. Chem. 2025, 21, 955–963, doi:10.3762/bjoc.21.79

• : the formation of compound 31 was always observed, and brevicolline ((±)-1) was not formed. Interestingly, our attempts made for the transformation of compound 31 by dehydrogenative aromatization to brevicolline ((±)-1) by using several reagents (DDQ, Pd/C, MnO2, CuCl2, I2, elemental sulfur, KMnO4

Copper-catalyzed domino cyclization of anilines and cyclobutanone oxime: a scalable and versatile route to spirotetrahydroquinoline derivatives

• Qingqing Jiang,
• Xinyi Lei,
• Pan Gao and
• Yu Yuan

Beilstein J. Org. Chem. 2025, 21, 749–754, doi:10.3762/bjoc.21.58

• to generate an enamine intermediate. Subsequently, an intermolecular cyclization occurs between the enamine and imine intermediates, ultimately yielding the final target product through an aromatization process (Scheme 4). Conclusion In summary, we have developed an efficient and practical copper

• intermediates, followed by intermolecular cyclization and aromatization. The scalability of this method was demonstrated through a gram-scale reaction, highlighting its potential for practical applications in medicinal chemistry and drug discovery. Synthetic strategies for the construction of

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

• substituted styrene under copper(I) catalysis to give the target compounds via a Povarov reaction. A further aromatization process yields product I (Scheme 8, path I). In a closely related approach, the same group reported on the synthesis of quinolines from anilines and alkynes [37]. In this case, the alkyne

• compound and MMS, undergoes an aza-Diels–Alder cyclization with the alkyne, and after oxidation and aromatization steps generates quinoline II. Unfortunately, under these gentle and greener conditions, aliphatic alkynes remain unreacted, compared to the metal-catalyzed version developed by Xu et al. [37

• reacts with the enolate of the ketone, which is stabilized by coordination with Fe(III), resulting in the formation of the C–C bond. A further oxidative aromatization process affords compound I. Compared to the protocol developed by Zhang et al. [24], the reaction is less regioselective, as Troger’s base

New tandem Ugi/intramolecular Diels–Alder reaction based on vinylfuran and 1,3-butadienylfuran derivatives

• Yuriy I. Horak,
• Roman Z. Lytvyn,
• Andrii R. Vakhula,
• Yuriy V. Homza,
• Nazariy T. Pokhodylo and
• Mykola D. Obushak

Beilstein J. Org. Chem. 2025, 21, 444–450, doi:10.3762/bjoc.21.31

• a coordinated mechanism. Noteworthy, the primary kinetic product of the cycloaddition reaction 5 is not transformed into the thermodynamic product 6 via a H-shift at the last stage. The expected aromatization with the formation of a furan ring, as happens in similar reactions, does not occur (Scheme

Recent advances in organocatalytic atroposelective reactions

• Henrich Szabados and
• Radovan Šebesta

Beilstein J. Org. Chem. 2025, 21, 55–121, doi:10.3762/bjoc.21.6

• -axial chirality conversion via catalyst-controlled oxidative aromatization [23]. In this way, the axially chiral starting material 12 comprising an additional stereogenic center was converted into oligonaphthylenes 13 with two, three or even four stereogenic axes. Based on the organocatalyst used, the

• was carried out to provide the final biaryl products 17. In a related strategy, Hayashi´s team realized an organocatalytic Michael/aldol cascade leading to chiral dihydronaphthalene derivatives 20a–e [25]. Through a series of one-pot reactions, aromatization was achieved with concomitant central-to

• -axial chirality conversion and formation of axially chiral products 21a–e (Scheme 7). This critical aromatization was later studied in more detail, and the team was able to achieve enantiodivergent aromatization, which led to different atropoisomers based on the oxidation reagent used [26]. The use of

Synthesis of tricarbonylated propargylamine and conversion to 2,5-disubstituted oxazole-4-carboxylates

• Kento Iwai,
• Akari Hikasa,
• Kotaro Yoshioka,
• Shinki Tani,
• Kazuto Umezu and
• Nagatoshi Nishiwaki

Beilstein J. Org. Chem. 2024, 20, 2827–2833, doi:10.3762/bjoc.20.238

• decarboxylation accompanied by aromatization of the oxazole ring occurred during this process. Thus, protonation occurs, leading to oxazole 5 when the reaction mixture is warmed in the presence of large amounts of proton sources such as acetic acid or deuterium oxide. Although Nagao et al. proposed another

Copper-catalyzed yne-allylic substitutions: concept and recent developments

• Shuang Yang and
• Xinqiang Fang

Beilstein J. Org. Chem. 2024, 20, 2739–2775, doi:10.3762/bjoc.20.232

• of ortho-aryl steric hindrance. Recently, Xu et al. [81] presents a copper-catalyzed asymmetric [4 + 1] annulation strategy, utilizing remote stereocontrol substitution/annulation/aromatization to forge arylpyrroles with various C–C (Scheme 49, 48a–h), C–N (Scheme 50, 49a–h) or 1,2-di- (Scheme 51

• stereoselective aromatization serves as a pivotal step in the transfer of central chirality to axial chirality (Scheme 52). To harness the full potential of CO2 as a renewable and abundant carbon source, He et al. [82] proposed an innovative strategy that married asymmetric yne-allylic substitution with CO2

Heterocycle-guided synthesis of m-hetarylanilines via three-component benzannulation

• Andrey R. Galeev,
• Maksim V. Dmitriev,
• Alexander S. Novikov and
• Andrey N. Maslivets

Beilstein J. Org. Chem. 2024, 20, 2208–2216, doi:10.3762/bjoc.20.188

• interrupted Kröhnke reaction (Scheme 1B) [51][52]. The main step of this process is an intermolecular cyclization of the formed 1,5-diketone followed by aromatization. Previously we have shown that 1,3-diketones bearing an electron-withdrawing group (EWG) adjacent to one of the carbonyls readily react with in

Efficacy of radical reactions of isocyanides with heteroatom radicals in organic synthesis

• Akiya Ogawa and
• Yuki Yamamoto

Beilstein J. Org. Chem. 2024, 20, 2114–2128, doi:10.3762/bjoc.20.182

• generates a stannylated imidoyl radical 20. The subsequent 5-exo cyclization, hydrogen abstraction from n-Bu3SnH, and aromatization successfully afforded the stannylated indole derivative 21 (Scheme 13) [8][54][55][56]. The stannyl group of 21 could be transferred to aryl or vinyl group by cross-coupling

• reaction of o-ethenylaryl isocyanides with disulfides in the presence of diphenyl ditelluride yields the corresponding dithiolated indole derivatives 23 (Scheme 16) [60]. Initially, the thiotelluration products via 5-exo cyclization are formed in situ. The subsequent aromatization followed by photoinduced

• addition of radical species to the isocyano group of 29 to form the imidoyl radical 30 as a key intermediate, which adds intramolecularly to the ortho-aryl group. The subsequent aromatization with the release of hydrogen (or proton) affords 31 in good yields. Nanni et al. reported the reaction of 2

Multicomponent syntheses of pyrazoles via (3 + 2)-cyclocondensation and (3 + 2)-cycloaddition key steps

• Ignaz Betcke,
• Alissa C. Götzinger,
• Maryna M. Kornet and
• Thomas J. J. Müller

Beilstein J. Org. Chem. 2024, 20, 2024–2077, doi:10.3762/bjoc.20.178

• . In cases where the α,β-unsaturated carbonyl compounds contain a heteroatom in the β-position, aromatization is triggered by elimination under redox-neutral conditions. Tasch et al. successfully coupled aryl halides with α-bromocinnamaldehyde (51) using a Masuda borylation Suzuki cross-coupling (MBSC

The Groebke–Blackburn–Bienaymé reaction in its maturity: innovation and improvements since its 21st birthday (2019–2023)

• Cristina Martini,
• Muhammad Idham Darussalam Mardjan and
• Andrea Basso

Beilstein J. Org. Chem. 2024, 20, 1839–1879, doi:10.3762/bjoc.20.162

Chemo-enzymatic total synthesis: current approaches toward the integration of chemical and enzymatic transformations

• Ryo Tanifuji and
• Hiroki Oguri

Beilstein J. Org. Chem. 2024, 20, 1693–1712, doi:10.3762/bjoc.20.151

• aromatization provides chalcone 43. Prenylation of the resultant aromatic ring of 43, catalyzed by MaIDT (Morus alba isoliquiritigenin 3-dimethylallyltransferase), leads to morachalcone A (44) [50][51]. In parallel, benzofuran 46 was biosynthesized from 4-coumaroyl-CoA via thioester 45. Further prenylation of