Silica gel with covalently attached bambusuril macrocycle for dicyanoaurate sorption from water

• Michaela Šusterová and
• Vladimír Šindelář

Beilstein J. Org. Chem. 2025, 21, 2604–2611, doi:10.3762/bjoc.21.201

• to SG not only by electrostatic interactions but also covalently, the BU1 synthesis is straightforward lacking difficult and time-consuming purification, and it is obtained in relatively high yield over 60%. Once BU1 was prepared, its covalent attachment on the surface of SG was achieved in two steps

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

• ]undec-7-ene (DBU) in benzene resulted in high yield of β-hydroxyaldehyde 6. Through a series of synthetic transformations, the target products (−)-taiwaniaquinones A (7), F (8), G (9), and H (11), (−)-taiwaniaquinol B (10) and (−)-dichroanone (12) were obtained from intermediate 6 (Scheme 2). An

• formation of a mixture of ketone 194 and cyclic diene 195. Regio- and stereoselectivity was observed in the case of the epoxide 189. The cyclopentane derivative 194 was obtained stereoselectively and in high yield during the reaction with BF3·Et2O. An alternative example of the tandem epoxide rearrangement

Pd-catalyzed dehydrogenative arylation of arylhydrazines to access non-symmetric azobenzenes, including tetra-ortho derivatives

• Loris Geminiani,
• Kathrin Junge,
• Matthias Beller and
• Jean-François Soulé

Beilstein J. Org. Chem. 2025, 21, 2234–2242, doi:10.3762/bjoc.21.170

• proved to be a suitable coupling partner, enabling the preparation of azoarene 3p in 70% yield. Moreover, starting from 1,4-dibromobenzene and 2 equivalents of 1a, a double reaction occurred, enabling the one-step synthesis of 1,4-bis[(E)-2-phenyldiazenyl]benzene (3q) in high yield. We next investigated

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

• solvent and Pd as catalyst played a vital role for achieving a high yield. Efficient subsequent esterification and quaternarization to diesterquat fabric softeners demonstrated that high-value chemicals could be produced fully biobased from GCA as the starting platform (Scheme 2). GCA can also be used as

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

• group [35][36][37]. This catalytic system efficiently overcame the challenge and furnished the coupling product 46 in high yield. Oxidative cleavage of the double bond in 46 followed by Mg(II)-mediated chelation-controlled Friedel–Crafts cyclization delivered secondary alcohol 47, which was elaborated

• donor, securing the desired secondary alcohol product in excellent enantioselectivity (99% ee). Protection of the alcohol group with TBDPSCl gave silyl ether 64 in high yield (79% for 2 steps). Subsequently, successive four manipulations including dehydrogenation, Morita–Baylis–Hillman reaction

• -catalyzed intermolecular Diels–Alder reaction of 106 with methacrolein 107 afforded the common intermediate 108 in high yield. Sequential Grignard reagent addition and acid-promoted ethoxy elimination provided the separable planar diene 109 (dr = 1:1), which underwent a Mn-catalyzed HAT hydrogenation to

Discovery of cytotoxic indolo[1,2-c]quinazoline derivatives through scaffold-based design

• Daniil V. Khabarov,
• Valeria A. Litvinova,
• Lyubov G. Dezhenkova,
• Dmitry N. Kaluzhny,
• Alexander S. Tikhomirov and
• Andrey E. Shchekotikhin

Beilstein J. Org. Chem. 2025, 21, 2062–2071, doi:10.3762/bjoc.21.161

• trifluoroacetic acid affords intermediate compound 6, bearing a trifluoroacetyl group on the indole moiety. Treatment of 6 with the base yielded the acid 3 in high yield (Scheme 2). The carboxyl group of 3 was converted to the corresponding amides via coupling with mono-N-Boc-protected C2–C4 diamines using PyBOP

Enantioselective desymmetrization strategy of prochiral 1,3-diols in natural product synthesis

• Lihua Wei,
• Rui Yang,
• Zhifeng Shi and
• Zhiqiang Ma

Beilstein J. Org. Chem. 2025, 21, 1932–1963, doi:10.3762/bjoc.21.151

• trifluoroacetic acid (TFA) and Ac2O, along with acetylation of the free hydroxy group, to deliver compound 239 in high yield. A further six-step sequence completed the synthesis of (−)-vincamajinine (240). With the same strategy, (−)-11-methoxy-17-epivincamajine (245) was prepared from (+)-Na-methyl-16

• genus) are generally operated in mild conditions achieving relatively high yield and enantioselectivity. However, due to the intrinsic structural limitations of lipases, accessing the desired enantiomer requires laborious screening of enzymes. In the case of transition-metal-catalyzed acylations, the

Synthesis of N-doped chiral macrocycles by regioselective palladium-catalyzed arylation

• Shuhai Qiu and
• Junzhi Liu

Beilstein J. Org. Chem. 2025, 21, 1917–1923, doi:10.3762/bjoc.21.149

• introduced. In contrast, when bulky 3,5-bis(trifluoromethyl)phenyl groups were introduced, only inherent chiral macrocyclic products (MC3) were obtained in high yield. Their molecular structures are unambiguously characterized by NMR, mass spectra and X-ray crystallographic characterization. In addition

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

• interactions with the enehydrazine intermediate, which is essential for achieving high levels of stereocontrol. Using the optimal catalyst CPA 1, a series of aza[6]helicenes 3a,b was synthesized with excellent enantioselectivity and high yield. However, this method demonstrated notably reduced efficiency and

• enantioselectivity. Conversely, employing macrocyclic paracyclophane with longer ansa chains (≥15 members) enabled efficient dynamic kinetic resolution due to the instable planar chirality of the substrates, which produced the planarly chiral macrocycles with high yield and enantioselectivity (up to 98% yield and 99

Influence of the cation in hypophosphite-mediated catalyst-free reductive amination

• Natalia Lebedeva,
• Fedor Kliuev,
• Olesya Zvereva,
• Klim Biriukov,
• Evgeniya Podyacheva,
• Maria Godovikova,
• Oleg I. Afanasyev and
• Denis Chusov

Beilstein J. Org. Chem. 2025, 21, 1661–1670, doi:10.3762/bjoc.21.130

• . The remedy for Parkinson’s disease, piribedil, was obtained in high yield. The plausible mechanism of the elaborated process was proposed and supported by DFT calculations. Keywords: amines; DFT; hypophosphites; reductive amination; role of cations; Introduction Sodium hypophosphite, NaH2PO2, is one

• , the synthesis of the remedy for Parkinson’s disease, piribedil (9), in high yield (80%) demonstrated the practical utility of the elaborated synthetic method (Figure 1). To get insight into the mechanism of the developed approach the reaction mixtures were thoroughly analyzed and several control

3-Aryl-2H-azirines as annulation reagents in the Ni(II)-catalyzed synthesis of 1H-benzo[4,5]thieno[3,2-b]pyrroles

• Julia I. Pavlenko,
• Pavel A. Sakharov,
• Anastasiya V. Agafonova,
• Derenik A. Isadzhanyan,
• Alexander F. Khlebnikov and
• Mikhail S. Novikov

Beilstein J. Org. Chem. 2025, 21, 1595–1602, doi:10.3762/bjoc.21.123

• under the Vilsmeier–Haack reaction conditions provided aldehyde 8 in high yield. To further assess the scope and limitations of the developed annulation protocol, we investigated the reactivity of aza-analogs of ester 1, indoles 9a‒c, toward azirine 2a under the same conditions. The reaction of N

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

• regioselectively for both methods. In most cases, the reactions proceeded with high yield and without the formation of significant byproducts. Results and Discussion Synthesis Hydantoins 2, containing an exocyclic C=N group, were synthesized according to the methodology described in [22] (Scheme 1). In brief, N,N

Ambident reactivity of enolizable 5-mercapto-1H-tetrazoles in trapping reactions with in situ-generated thiocarbonyl S-methanides derived from sterically crowded cycloaliphatic thioketones

• Grzegorz Mlostoń,
• Małgorzata Celeda,
• Marcin Palusiak,
• Heinz Heimgartner,
• Marta Denel-Bobrowska and
• Agnieszka B. Olejniczak

Beilstein J. Org. Chem. 2025, 21, 1508–1519, doi:10.3762/bjoc.21.113

• (mp 136‒138 °C) in high yield of 86%. The 13C NMR spectrum registered for this compound revealed a shift of the S‒C‒S atom, incorporated into the cyclobutanone ring, at 74.8 ppm. On the other hand, the thioaminal functionality with N‒C‒S moiety located within the tetrazole ring, shows a signal at

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

Recent advances and future challenges in the bottom-up synthesis of azulene-embedded nanographenes

• Bartłomiej Pigulski

Beilstein J. Org. Chem. 2025, 21, 1272–1305, doi:10.3762/bjoc.21.99

• exceptionally high yield (97%). A Suzuki cross-coupling reaction between 47 and 45 gave compound 48 which was subjected to a final Scholl oxidation using DDQ. The target compound 49, containing two azulene subunits, was obtained in a relatively low yield (16%). Analysis of NICS values for 49 revealed similar

• oxidation of azulene units is particularly efficient when performed in an electron-deficient system, as demonstrated by Tani and co-workers [71] in their synthesis of azulene-fused tetracene diimide 107 from precursor 106 (Scheme 15). Oxidation with DDQ gave the target product in very high yield (95

• authors attempted to directly oxidize 170 to 172 using Scholl reaction. However, compound 172 was isolated in only 1% yield. As an alternative, they brominated 170 to form 171, followed by Yamamoto-type coupling using Ni(COD)2 and 2,2’bipirydyl (COD = 1,5-cyclooctadiene), which produced 172 in high yield

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

• the trend C–I > C–Br > C–Cl, consistent with bond dissociation energies (90g–j). Notably, deuterated chloroform was successfully employed to obtain deuterated oxindole 90k in high yield, demonstrating the method's potential for isotope labeling applications. A plausible mechanism, as outlined in

Synthetic approach to borrelidin fragments: focus on key intermediates

• Yudhi Dwi Kurniawan,
• Zetryana Puteri Tachrim,
• Teni Ernawati,
• Faris Hermawan,
• Ima Nurasiyah and
• Muhammad Alfin Sulmantara

Beilstein J. Org. Chem. 2025, 21, 1135–1160, doi:10.3762/bjoc.21.91

• reacting it with Eschenmoser’s salt, followed by hydrolysis with lithium hydroxide. The resulting unsaturated acid 54, isolated in 92% yield, underwent asymmetric hydrogenation using both (Ra)-50 and (Sa)-50 catalysts. This step provided the respective compounds 55 and 56 in excellent high yield and

• demonstrated when compound 100 was treated with MeMgBr/CuBr and either 94 or ent-94, affording 101a and 101b, respectively, with high yield and exclusive diastereoselectivity. Compound 101a, featuring the relevant stereochemistry of borrelidin at the C4, C6, C8, and C10, underwent Baeyer–Villiger oxidation

Investigations of amination reactions on an antimalarial 1,2,4-triazolo[4,3-a]pyrazine scaffold

• Henry S. T. Smith,
• Ben Giuliani,
• Kanchana Wijesekera,
• Kah Yean Lum,
• Sandra Duffy,
• Aaron Lock,
• Jonathan M. White,
• Vicky M. Avery and
• Rohan A. Davis

Beilstein J. Org. Chem. 2025, 21, 1126–1134, doi:10.3762/bjoc.21.90

• ]pyrazine was explored here for phenethylamine and 13 other liquid primary amines. This convenient synthesis involving only addition of liquid amine to starting material, and stirring at room temperature, was found to proceed readily within 6 to 16 h, in generally high yield. Exclusive tele-substitution (8

A versatile route towards 6-arylpipecolic acids

• Erich Gebel,
• Cornelia Göcke,
• Carolin Gruner and
• Norbert Sewald

Beilstein J. Org. Chem. 2025, 21, 1104–1115, doi:10.3762/bjoc.21.88

• acid (7-ACA) from cephalosporin C by cephalosporin C acylase [37], was used as a chiral starting material. After esterification of both carboxylic acid functions followed by cyclization to the lactam [38][39], the six-membered ring structure was established as (R)-methyl 6-oxopipecolate (7) with a high

• yield of 88%. (R)-Methyl 6-oxopipecolate (7) was converted under Vilsmeier–Haack conditions [35][40][41] to undergo N-formylation and concomitant enol bromination to give product 2 (Scheme 2). Due to slow degradation of the bromide 2, the subsequent cross-coupling reaction was conducted immediately

Pd-Catalyzed asymmetric allylic amination with isatin using a P,olefin-type chiral ligand with C–N bond axial chirality

• Natsume Akimoto,
• Kaho Takaya,
• Yoshio Kasashima,
• Kohei Watanabe,
• Yasushi Yoshida and
• Takashi Mino

Beilstein J. Org. Chem. 2025, 21, 1018–1023, doi:10.3762/bjoc.21.83

• obtained (S)-13k in good yield with moderate enantioselectivity. Furthermore, when (E)-1,3-di(p-chlorophenyl)-2-propenyl acetate (15) was utilized as an allylic acetate, the desired product (S)-13l was obtained in high yield with excellent enantioselectivity. We confirmed that the product 13 from the Pd

Recent total synthesis of natural products leveraging a strategy of enamide cyclization

• Chun-Yu Mi,
• Jia-Yuan Zhai and
• Xiao-Ming Zhang

Beilstein J. Org. Chem. 2025, 21, 999–1009, doi:10.3762/bjoc.21.81

• -silyl substituted cyclopentanone 41, and acyl chloride 42 produced enamide 43. The polycyclization then took place under the catalysis of Cu(OTf)2/L3 and In(OTf)3, delivering tricyclic product 44 in high yield with excellent enantioselectivity. Despite formation of multiple diastereomers due to the

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

Regioselective formal hydrocyanation of allenes: synthesis of β,γ-unsaturated nitriles with α-all-carbon quaternary centers

• Seeun Lim,
• Teresa Kim and
• Yunmi Lee

Beilstein J. Org. Chem. 2025, 21, 800–806, doi:10.3762/bjoc.21.63

• converted to the desired nitrile 5g in high yield. Gram-scale reactions were conducted using allenes to demonstrate the practical applicability of this hydrocyanation method (Scheme 5). Allene 1q (1.04 g, 7.2 mmol) and allene 4b (1.08 g, 6.0 mmol) were effectively transformed into nitrile products 3q and 5b

Recent advances in the electrochemical synthesis of organophosphorus compounds

• Babak Kaboudin,
• Milad Behroozi,
• Sepideh Sadighi and
• Fatemeh Asgharzadeh

Beilstein J. Org. Chem. 2025, 21, 770–797, doi:10.3762/bjoc.21.61

• activities. Budnikova et al. [50] reported a C–P bond formation via the reaction of acridine compounds with trialkyl phosphites in electrochemical conditions without metal catalysts and strong oxidizing reagents, conducting selective C9 phosphorylation with high yield. The reaction was carried out in an

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

• optimization revealed LiOt-Bu and diphenyl phosphate as the optimal metal alkoxide and leaving group, delivering the desired product 32 in high yield and high enantioselectivity at room temperature with only 2 mol % catalyst loading. The scope of this transformation proved to be remarkably broad. In addition