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

• the perhydrindanic structure. In contrast, the use of Al-H-Na-Lar pillared clay [90] as a heterogeneous catalyst and heating in 2-nitropropane at 100 °C induced angular methyl migration with formation of the halimanic bicyclic system 203 [90]. The acid-induced rearrangement of the drimanic epoxide 201

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

• of levulinic acid-derived molecules. The same group later reported a more active heterogeneous catalyst, Ru–MnOx/Al2O3, providing 2-butanol with yields up to 98.8% [242]. Conversion to 2-methyltetrahydrofuran: 2-Methyltetrahydrofuran is a promising biofuel with high energy density, high stability and

Microwave-enhanced additive-free C–H amination of benzoxazoles catalysed by supported copper

• Andrei Paraschiv,
• Valentina Maruzzo,
• Filippo Pettazzi,
• Stefano Magliocco,
• Paolo Inaudi,
• Daria Brambilla,
• Gloria Berlier,
• Giancarlo Cravotto and
• Katia Martina

Beilstein J. Org. Chem. 2025, 21, 1462–1476, doi:10.3762/bjoc.21.108

• development of heterogeneous catalysis has faced challenges, due to uncertainties around catalytic sites, aggregation, and the leaching of active species during reactions. The use of a heterogeneous catalyst can greatly simplify the work-up process, as the catalyst can be easily removed via simple filtration

• supported copper(II) catalysts on covalently modified silica [51][52], we have set out to develop a new heterogeneous catalyst with atomically distributed active sites for the mild and efficient C–H amination of benzoxazole. This approach was chosen because the silica derivatisation and copper deposition

• groupds [68], while still retaining the ability of a Schiff base to efficiently bind transition metals, including copper [69]. An advantage of using a heterogeneous catalyst, beyond the easy filtration from the reaction mixture, lies in its possible reuse, multiple times, directly or after performing

Chitosan-supported CuI-catalyzed cascade reaction of 2-halobenzoic acids and amidines for the synthesis of quinazolinones

• Xuhong Zhao,
• Weishuang Li,
• Mengli Yang,
• Bojie Li,
• Yaoyao Zhang,
• Lizhen Huang and
• Lei Zhu

Beilstein J. Org. Chem. 2025, 21, 839–844, doi:10.3762/bjoc.21.67

• efficient, reusable heterogeneous catalyst for this cascade reaction, achieving good to excellent yields without any loss of activity even after ten cycles of simple filtration-based recovery [12]. Moreover, a copper catalyst has been shown to function effectively in both organic and aqueous media [13][14

Advances in radical peroxidation with hydroperoxides

• Oleg V. Bityukov,
• Pavel Yu. Serdyuchenko,
• Andrey S. Kirillov,
• Gennady I. Nikishin,
• Vera A. Vil’ and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2024, 20, 2959–3006, doi:10.3762/bjoc.20.249

• copper catalysis the complex Cu(II)OO-t-Bu was proposed [122]. The difunctionalization of styrenes 175 with trifluoromethyl and peroxy groups was carried out using Togni reagent II (176) as a CF3-group precursor and the metal organic framework Cu3(BTC)2 as a heterogeneous catalyst (Scheme 54) [123]. The

Synthesis of spiroindolenines through a one-pot multistep process mediated by visible light

• Francesco Gambuti,
• Jacopo Pizzorno,
• Chiara Lambruschini,
• Renata Riva and
• Lisa Moni

Beilstein J. Org. Chem. 2024, 20, 2722–2731, doi:10.3762/bjoc.20.230

• -pot multistep synthesis of unprecedent 2,3-diaminoindolenines using graphene oxide (GO) as heterogeneous catalyst [21]. The protocol involves the three-component Ugi (3C-Ugi) reaction between aldehydes, isocyanides and 2 equivalents of electron-rich anilines to give α-aminoamidines, which undergo a C

• ] 3. Based on our experience on the use of graphene oxide (GO) as heterogeneous catalyst to promote MCRs and subsequent C–N bond oxidation [16][21], we first investigated the GO-promoted oxidation of N-Ph-THIQ and the subsequent 3C Ugi reaction to give α-aminoamidine 2a. Applying the previously

Computational design for enantioselective CO₂ capture: asymmetric frustrated Lewis pairs in epoxide transformations

• Maxime Ferrer,
• Iñigo Iribarren,
• Tim Renningholtz,
• Ibon Alkorta and
• Cristina Trujillo

Beilstein J. Org. Chem. 2024, 20, 2668–2681, doi:10.3762/bjoc.20.224

• performance, for example, the reaction rate, is displayed as a function of the catalyst–substrate interaction, for example, the adsorption energy when considering a heterogeneous catalyst (Figure 1A). The resulting plot exhibits a volcano-like shape consisting of at least two slopes with the best-performing

Factors influencing the performance of organocatalysts immobilised on solid supports: A review

• Zsuzsanna Fehér,
• Dóra Richter,
• Gyula Dargó and
• József Kupai

Beilstein J. Org. Chem. 2024, 20, 2129–2142, doi:10.3762/bjoc.20.183

• influence on the properties and thus performance of the resulting heterogeneous catalyst. However, immobilisation and structural modification introduce additional steps in the synthesis of the catalyst. Moreover, the catalytic activity and selectivity of immobilised catalysts are often lower than those of

Green and sustainable approaches for the Friedel–Crafts reaction between aldehydes and indoles

• Periklis X. Kolagkis,
• Eirini M. Galathri and
• Christoforos G. Kokotos

Beilstein J. Org. Chem. 2024, 20, 379–426, doi:10.3762/bjoc.20.36

• of Fe3O4 nanoparticles (Scheme 15) [101][102]. This organic–inorganic hybrid material was synthesized by the immobilization of the dodecatungstovanadophosphoric acid (HPA) on TPI-Fe3O4 with N-[3-(triethoxysilyl)propyl]isonicotinamide (TPI), acting as the linker for the heterogeneous catalyst, while

• introduced nano n-propylsulfonated γ-Fe2O3 (NPS-γ-Fe2O3), which constitutes a magnetically recyclable heterogeneous catalyst that works in the exact same manner as HPA/TPI-Fe3O4 [103]. Some small differences between the two methods were the ability of ketones to form the respective BIMs, when NPS-γ-Fe2O3 was

Application of N-heterocyclic carbene–Cu(I) complexes as catalysts in organic synthesis: a review

• Nosheen Beig,
• Varsha Goyal and
• Raj K. Bansal

Beilstein J. Org. Chem. 2023, 19, 1408–1442, doi:10.3762/bjoc.19.102

• having a triisopropoxy(propyl)silyl ((-CH2)3Si(OiPr)3) substituent on the imidazole ring through in situ transmetallation. One of these complexes, 78a, was successfully anchored on mesoporous silica MCM-41 to afford a new heterogeneous catalyst (Scheme 27). Both compounds were subsequently used as

• . Unexpectedly, no reaction occurred when complex 78 anchored on mesoporous silica 78a-MCM-41 was used as heterogeneous catalyst. 2.2 Conjugate addition The conjugate addition is a reaction in which a nucleophile attacks at the β-position of an activated C=C moiety to give an addition product (Scheme 39). As

• benzyl azide with phenylacetylene (Scheme 52) [39]. In contrast to the hydrosilylation reaction (see section 2.1), both complexes catalyzed the cycloaddition reaction; however, the heterogeneous catalyst was found to be less active than the homogeneous catalyst. Straub and co-workers [70] in 2016 instead

Clauson–Kaas pyrrole synthesis using diverse catalysts: a transition from conventional to greener approach

• Dileep Kumar Singh and
• Rajesh Kumar

Beilstein J. Org. Chem. 2023, 19, 928–955, doi:10.3762/bjoc.19.71

• , Hosseini-Sarvari and co-workers [72] described a new and greener Clauson–Kaas method for the synthesis of N-substituted pyrroles 41 in 80–98 % yields by condensing 2,5-DMTHF (2) with amines 40 in the presence of the novel heterogeneous catalyst nano-sulfated TiO2 under solvent-free conditions (Scheme 19

• ] used the heterogeneous catalyst H3PW12O40/SiO2 for the Clauson–Kaas synthesis of N-substituted pyrrole derivatives 63 (Scheme 30) by the reaction of amines 62 with 2,5-dimethoxytetrahydrofuran (2) in petroleum ether at reflux conditions in 60–93% yields (method 1) and MW-assisted solvent-free

• 2.5 mol % HPA/SiO2 as catalyst, solventless under MW irradiation. The main advantages of this protocol is its greener, eco-friendly, stable and reusable heterogeneous catalyst, smooth and selective reaction under solvent-free conditions, excellent yields of products, easy work-up and simple handling

Derivatives of benzo-1,4-thiazine-3-carboxylic acid and the corresponding amino acid conjugates

• Péter Kisszékelyi,
• Tibor Peňaška,
• Klára Stankovianska,
• Mária Mečiarová and
• Radovan Šebesta

Beilstein J. Org. Chem. 2022, 18, 1195–1202, doi:10.3762/bjoc.18.124

• 1,3-dicarbonyl compounds using a catalytic amount of hydrazine hydrate without solvent in a short reaction time (10 min) [14]. Reactions of 2-aminothiophenols with β-keto esters and β-diketones under microwave irradiation (MWI) using basic alumina as heterogeneous catalyst without solvent afforded 4H

Heterogeneous metallaphotoredox catalysis in a continuous-flow packed-bed reactor

• Wei-Hsin Hsu,
• Susanne Reischauer,
• Peter H. Seeberger,
• Bartholomäus Pieber and
• Dario Cambié

Beilstein J. Org. Chem. 2022, 18, 1123–1130, doi:10.3762/bjoc.18.115

• and scalable reaction conditions. Here, we report a continuous-flow approach to metallaphotoredox catalysis using a heterogeneous catalyst that combines the function of a photo- and a nickel catalyst in a single material. The catalyst is embedded in a packed-bed reactor to combine reaction and

• processes [5] (Figure 1d): The heterogeneous catalyst remains located in a specific part of the reactor through which the reaction mixture is pumped, which reduces material damage through attrition and the confinement of the catalysts in the packed bed lifts the need for solid separation. If the catalyst is

• (12 h, in agreement with previous observations, see Figure 4a), only a minor decrease in the catalyst activity (about 1% per day) was observed throughout the experiment, demonstrating the good long-term stability of the heterogeneous catalyst. In particular, the catalyst turnover number (TON

Electrochemical hydrogenation of enones using a proton-exchange membrane reactor: selectivity and utility

• Koichi Mitsudo,
• Haruka Inoue,
• Yuta Niki,
• Eisuke Sato and
• Seiji Suga

Beilstein J. Org. Chem. 2022, 18, 1055–1061, doi:10.3762/bjoc.18.107

• consists of a membrane called a membrane electrode assembly (MEA), which can act as supporting electrolyte, electrode, and heterogeneous catalyst. Therefore, the further addition of a supporting electrolyte is not necessary for the electrochemical reactions using a PEM reactor, which offers clean and

Inductive heating and flow chemistry – a perfect synergy of emerging enabling technologies

• Conrad Kuhwald,
• Sibel Türkhan and
• Andreas Kirschning

Beilstein J. Org. Chem. 2022, 18, 688–706, doi:10.3762/bjoc.18.70

• second variant is the steam methane reforming process. Since complex solids such as wood, sewage sludge or municipal waste cannot be evaporated, they are reformed using supercritical water on a heterogeneous catalyst at 250–300 bar, 400–550 °C, and a large excess of water [28]. The former process is the

Heteroleptic metallosupramolecular aggregates/complexation for supramolecular catalysis

• Prodip Howlader and
• Michael Schmittel

Beilstein J. Org. Chem. 2022, 18, 597–630, doi:10.3762/bjoc.18.62

• of the guest molecule was proven by UV–vis and IR spectroscopy. The multicomponent prism (Figure 3) was finally utilized as a heterogeneous catalyst for Michael and Diels–Alder (DA) reactions in water, representing an uncommon hydrogen-bond donating heterogeneous catalyst [59]. Intrigued by the

Silica gel and microwave-promoted synthesis of dihydropyrrolizines and tetrahydroindolizines from enaminones

• Robin Klintworth,
• Garreth L. Morgans,
• Stefania M. Scalzullo,
• Charles B. de Koning,
• Willem A. L. van Otterlo and
• Joseph P. Michael

Beilstein J. Org. Chem. 2021, 17, 2543–2552, doi:10.3762/bjoc.17.170

• –hexane mixtures. Yields in toluene or xylene were typically around 90% (Table 1, entries 25 and 26). Although most reported microwave-promoted organic reactions on solid supports are performed without additional solvent [46][47], the combination of a nonpolar solvent with a polar heterogeneous catalyst

A recent overview on the synthesis of 1,4,5-trisubstituted 1,2,3-triazoles

• Pezhman Shiri,
• Ali Mohammad Amani and
• Thomas Mayer-Gall

Beilstein J. Org. Chem. 2021, 17, 1600–1628, doi:10.3762/bjoc.17.114

• aryl iodides containing electron-donating and electron-withdrawing groups exhibited good to excellent results in the reaction. Notably, the yield of the Click reaction with 2-iodotoluene decreased due to the steric effects. Moreover, the utilization of an efficient heterogeneous catalyst and

A comprehensive review of flow chemistry techniques tailored to the flavours and fragrances industries

• Guido Gambacorta,
• James S. Sharley and
• Ian R. Baxendale

Beilstein J. Org. Chem. 2021, 17, 1181–1312, doi:10.3762/bjoc.17.90

• . In 2008, the group of Sartori developed a flow setup for nitroaldol condensations of different benzaldehydes exploiting a silica-supported amine (KG-60-NH2) as a heterogeneous catalyst (Scheme 21) [133]. Secondary and tertiary amine-supported catalysts were also investigated, although they were found

• coated multichannel microreactor with an integrated zeolite ZSM-5 membrane (Scheme 28) [156][157]. The heterogeneous catalyst used was a Cs-exchanged faujasite NaX. The membrane maximised the outcomes in comparison to tested fixed-bed and microreactors. The ZSM-5 membrane allowed fast water exclusion

Recent advances in palladium-catalysed asymmetric 1,4–additions of arylboronic acids to conjugated enones and chromones

• Jan Bartáček,
• Jan Svoboda,
• Martin Kocúrik,
• Jaroslav Pochobradský,
• Alexander Čegan,
• Miloš Sedlák and
• Jiří Váňa

Beilstein J. Org. Chem. 2021, 17, 1048–1085, doi:10.3762/bjoc.17.84

• and with a very small amount of the catalyst needed (Table 28). The heterogeneous catalyst PdL10b system worked significantly better than the conventional homogeneous synthesis, even when using a significantly higher amount of the PdL10a catalytic species in the homogeneous system. The results were

• excellent both in terms of enantioselectivities and conversions (up to 98%; up to 83% ee; Table 28). The reuse of the heterogeneous catalyst has not been studied in this case. In 2020, our group reported the first heterogeneous polystyrene-supported recyclable catalyst for the asymmetric conjugate additions

Microwave-assisted multicomponent reactions in heterocyclic chemistry and mechanistic aspects

• Shivani Gulati,
• Stephy Elza John and
• Nagula Shankaraiah

Beilstein J. Org. Chem. 2021, 17, 819–865, doi:10.3762/bjoc.17.71

• and selective heating of the heterogeneous catalyst [20][21][22][23]. Even though the MWA technology is advantageous, a major challenge posed is the scale-up at the industry level where protocol efficiency at kilogram scale is mandatory. With rapid heat generation, and litres of solvents often safety

• reusability of the heterogeneous catalyst is also an advantage of the stated strategy. The higher yields >82% obtained from the microwave-assisted protocol reveal its competency over the conventional method (79%) along with the time parameter wherein the time was reduced from hours to just minutes (6 h to 20

Valorisation of plastic waste via metal-catalysed depolymerisation

• Francesca Liguori,
• Carmen Moreno-Marrodán and
• Pierluigi Barbaro

Beilstein J. Org. Chem. 2021, 17, 589–621, doi:10.3762/bjoc.17.53

A novel and robust heterogeneous Cu catalyst using modified lignosulfonate as support for the synthesis of nitrogen-containing heterocycles

• Bingbing Lai,
• Meng Ye,
• Ping Liu,
• Minghao Li,
• Rongxian Bai and
• Yanlong Gu

Beilstein J. Org. Chem. 2020, 16, 2888–2902, doi:10.3762/bjoc.16.238

• ; heterogeneous catalyst; immobilized copper catalyst; lignosulfonate; nitrogen-containing heterocycles; solid acid; Introduction Heterogeneous metal catalysts have been continuously receiving considerable attention in the field of organic synthesis owing to the advantages of easy separation and recycling [1][2

• -Cu-promoted conditions as well, and gave the product 4o in 65% yield. The successful attempts in the three-component reaction of 4-aminoindoles (1a), alkynes and aldehydes indicate that the heterogeneous catalyst LS-FAS-Cu is competent for catalyzing nitrogen-containing heterocyclic compounds without

Palladium nanoparticles supported on chitin-based nanomaterials as heterogeneous catalysts for the Heck coupling reaction

• Tony Jin,
• Malickah Hicks,
• Davis Kurdyla,
• Sabahudin Hrapovic,
• Edmond Lam and
• Audrey Moores

Beilstein J. Org. Chem. 2020, 16, 2477–2483, doi:10.3762/bjoc.16.201

• Mining and Materials Engineering, McGill University, Montreal, Quebec H3A 0E9, Canada 10.3762/bjoc.16.201 Abstract In this report, chitin and chitosan nanocrystals were used as biomass-based supports for Pd nanoparticles (NPs) used as a heterogeneous catalyst for the Heck coupling reaction. By using a

Natural dolomitic limestone-catalyzed synthesis of benzimidazoles, dihydropyrimidinones, and highly substituted pyridines under ultrasound irradiation

• Kumar Godugu,
• Venkata Divya Sri Yadala,
• Mohammad Khaja Mohinuddin Pinjari,
• Trivikram Reddy Gundala,
• Lakshmi Reddy Sanapareddy and
• Chinna Gangi Reddy Nallagondu

Beilstein J. Org. Chem. 2020, 16, 1881–1900, doi:10.3762/bjoc.16.156

• . Conclusion An environmentally benign NDL catalyst was characterized and utilized as a heterogeneous catalyst for the synthesis of 2-aryl-1-arylmethyl-1H-benzo[d]imidazoles, dihydropyrimidinones/ -thiones, and 2-amino-4-(hetero)aryl-3,5-dicarbonitrile-6-sulfanylpyridines in a mixture of ethanol and H2O 1:1