Photoorganocatalytic trifluoromethylation of (het)arenes in green conditions

• Egor N. Boronin,
• Svetlana E. Kaurkina,
• Milena M. Svetlakova,
• Anton S. Bolshakov,
• Maxim V. Arsenyev,
• Vasilii F. Otvagin,
• Alexey Yu. Fedorov,
• Timothy Noël and
• Alexander V. Nyuchev

Beilstein J. Org. Chem. 2026, 22, 662–671, doi:10.3762/bjoc.22.50

• -catalyzed [8], organic photocatalyst-mediated, or electrochemical transformations [9], and also include continuous-flow processes [6][10][11][12][13]. Given that photocatalytic reactions align with the principles of green chemistry, particularly energy efficiency and the use of catalytic pathways, such

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

• 289, 9000 Gent, Belgium 10.3762/bjoc.22.48 Abstract The first NHC–Cu-catalyzed decomposition of formic acid (FA) is reported. In the presence of PhSiH3, only hydrogen is generated while CO2 is captured by a silane species. The decomposition of an equimolar mixture of FA and an amine provided an

• performances than copper salts, even with lower catalyst loading and under milder conditions [49][50][51]. Based on this background, the first potential formic acid dehydrogenation catalyzed by NHC–Cu complexes (Figure 1) was investigated. Results and Discussion We have shown that the reaction of [Cu(OH)(IPr

• experiments were carried out (Scheme 2). By reacting FA and PhSiH3 (1:1 molar ratio) in the presence of 10 mol % of 1a, in deuterated toluene at room temperature under D2 atmosphere (1 atm), no H–D scrambling was observed (Scheme 2a). Furthermore, the 1a-catalyzed reaction of FA labeled at the acidic position

Regioselective approach to 5-arylsulfonylisoxazoles and their antimicrobial activity

• Artem S. Sazonov,
• Dmitry A. Vasilenko,
• Denis V. Porfiriev,
• Yuri K. Grishin,
• Rimma A. Gazzaeva,
• Alisa P. Chernyshova,
• Maxim A. Kryakvin,
• Anna A. Baranova,
• Vera A. Alferova and
• Elena B. Averina

Beilstein J. Org. Chem. 2026, 22, 592–602, doi:10.3762/bjoc.22.45

• 4-unsubstituted isoxazoles with various aryl substituents in position 3 [24][25] (approach B). One example describes the Ru-catalyzed reaction of nitrile oxide with alkynyl sulfone providing 5-sulfonylisoxazole with high regioselectivity [26] (approach C). Despite the widespread application of

Continuous-flow carbonyl hydrogenation under subatmospheric to atmospheric hydrogen pressure enabled by robust heterogeneous Pt–Fe catalysts

• Hiroyuki Miyamura,
• Ryosuke Kajiyama,
• Shun-ya Onozawa,
• Yoshihiro Kon and
• Shū Kobayashi

Beilstein J. Org. Chem. 2026, 22, 575–582, doi:10.3762/bjoc.22.43

• might be reduced by NaBH4 faster than FeCl2 in the solution phase, and the generated Pt(0) nanoparticles are stabilized by DMPSi surface. The reduction of FeCl2, which is usually more difficult to achieve can be catalyzed on the surface of Pt(0) nanoparticles and the formed Fe species are deposited and

Kinetic resolution of racemic planar-chiral vinylcymantrenes by molybdenum-catalyzed asymmetric metathesis dimerization

• Haruna Imazu,
• Hitoshi Izu,
• Yasuhiro Ohki and
• Masamichi Ogasawara

Beilstein J. Org. Chem. 2026, 22, 568–574, doi:10.3762/bjoc.22.42

• ) reaction catalyzed by a chiral molybdenum-alkylidene precatalyst. The Mo/(R)-L1 precatalyst promoted the AMD/KR reaction of rac-1a (R = Br) to give (E)-(R,R)-2a of 99% ee together with unreacted recovered (S)-1a of 45% ee at 37% conversion. The diastereoselectivity of this reaction was excellent with

• ], racemic 5a–c were prepared in the same ways starting with rac-3. Vinylcymantrene substrates rac-1a–c were obtained in 68–79% yields by the Wittig methylenation of rac-5a–c. The moderate yields could be attributed to the volatility of rac-1a–c. Molybdenum-catalyzed asymmetric metathesis dimerization (AMD

• metathesis dimerization of (R)-1a preferentially, and the most of antipodal (S)-1a was recovered intact. In general, vinylcymantrenes are much less reactive than analogous vinylferrocenes in the molybdenum-catalyzed AMD [30], and the conversion tends to be lower. Only 25% conversion was attained in the

Experimental and DFT studies on the regioselective methanolysis of 5-azido-9-oxabicyclo[6.1.0]nonan-4-yl 4-nitrobenzoate isomers

• İlknur Polat,
• Selçuk Eşsiz and
• Emine Salamci

Beilstein J. Org. Chem. 2026, 22, 547–556, doi:10.3762/bjoc.22.40

• , pharmaceutical compounds, and chiral ligands. The Lewis acid-catalyzed ring-opening reaction of cyclohexene oxide by MeZH (Z = O, S, and NH) is well known [20]. However, studies on large-sized bicyclic epoxides remain relatively limited in the published literature. In our previous study, we performed the ring

Get a better glimpse on sequential photoreactions of trisnorbornadienes with ¹⁹F NMR spectroscopy

• Julian Felix Maria Hebborn,
• Ben Eric Merten,
• Thomas Paululat and
• Heiko Ihmels

Beilstein J. Org. Chem. 2026, 22, 527–534, doi:10.3762/bjoc.22.38

• almost quantitative (see Supporting Information File 1, Figures S13 and S14). To gain more information about the course of the photoreaction and sequential formation of intermediates, the photoreaction of 1f, catalyzed by flavin 4, was investigated with in situ 19F NMR-spectroscopic analysis. During the

Modern synthetic pathways towards eribulin and its subunits

• Sebastian Dominik Graf

Beilstein J. Org. Chem. 2026, 22, 495–526, doi:10.3762/bjoc.22.37

• towards 113 upon acidic treatment and TBDMS-protection. Reduction, cleavage of the silyl-protecting groups and acetylation led to tetrahydropyran 114. Lewis acid-catalyzed C-allylation, cross metathesis, basic cleavage of the acetate motifs and transesterification enabled the DBU-induced isomerization of

• . Scaling up the Grubbs metathesis of the first route (Scheme 10, step (h) i.) led to an increasement of dimer yield derived from cross metathesis reactions. Therefore, by the replacement with the Rh(I)-catalyzed cyclization performed herein, this drawback is circumvented and the reactions were performed

• to afford 154. Allylation and acidic deprotection led to diol 156 in excellent yields. Next, Au(I)-catalyzed cyclization and reduction led to tetrahydropyran 157, which was TBDMS-protected subsequently. The cross metathesis of 158 and 162 (obtained from ʟ-glutamic acid) yielded 159 in 81%. After

Synthesis and uranyl(VI) extraction performance of a calix[4]pyrrole–tetrahydroxamic acid receptor

• Sara Karnib,
• Rana Baydoun,
• Wissam Zaidan,
• Nancy AlHaddad,
• Omar El Samad,
• Bilal Nsouli,
• Francine Cazier-Dennin and
• Pierre-Edouard Danjou

Beilstein J. Org. Chem. 2026, 22, 486–494, doi:10.3762/bjoc.22.36

• -hydroxyphenyl)calix[4]pyrrole, commonly referred to as phenoxycalix[4]pyrrole (PCP). It was first reported in 1999 by two independent research groups, Floriani et al. and Sessler et al., via the acid-catalyzed condensation of pyrrole with p-hydroxyacetophenone [17][18]. PCP and its derivatives were first known

Recent advances in the stereoselective synthesis of distal biaxially chiral molecules

• Fanxing Zhou,
• Chen Zhang,
• Lingyu Sun,
• Yiyun Fang,
• Siming Zheng,
• Lina Hu,
• Mengyang Shen,
• Zhen Zhao,
• Wei Xu,
• Yunqiang Sun and
• Zi-Qiang Rong

Beilstein J. Org. Chem. 2026, 22, 461–479, doi:10.3762/bjoc.22.34

• , Hayashizaki, and Ito reported a highly stereoselective asymmetric cross-coupling reaction of 2-methylnaphthylmagnesium bromide with bromonaphthalene, catalyzed by a nickel complex with ferrocenylphosphine as the ligand, successfully synthesizing biaxially chiral molecules, namely 1,1':5',1"- and 1,1':4',1

• demonstrated that such one-step catalytic approaches not only streamline the synthesis of structurally complex biaxial molecules but also open new avenues for their applications in catalysis, drug discovery, and functional materials. In 2004, Shibata and co-workers reported a novel iridium-catalyzed asymmetric

• , transition-metal-catalyzed approach for the synthesis of helically chiral polyaryl compounds with well-defined sequences of axial chirality. Using this method, they successfully obtained pentaaryl 6 (Scheme 1b) and nonaryl derivatives (not shown) bearing four and eight consecutive chiral axes, respectively

Cone p-aminocalix[4]arenes enriched with ‘clickable’ alkyne or azide functionalities

• Ilia Korniltsev,
• Vasily Bazhenov,
• Alexander Gorbunov,
• Dmitry Cheshkov,
• Stanislav Bezzubov,
• Vladimir Kovalev and
• Ivan Vatsouro

Beilstein J. Org. Chem. 2026, 22, 399–415, doi:10.3762/bjoc.22.28

• conversion into diverse 1,4-disubstituted 1,2,3-triazole units under CuAAC (copper(I)-catalyzed azide–alkyne cycloaddition) ‘click’ conditions [70][71][72][73]. The first implementation of the CuAAC approach for calixarene modification was published shortly after its introduction into chemistry in general

• to be not bulky enough to protect the alkyne from a Raney-Ni-catalyzed reduction by gaseous hydrogen, as a trial hydrogenation of the nitrated/propargylated calix[4]arene 11 resulted in only trace amounts of the desired p-aminocalix[4]arene 18 among numerous other reaction products. Due to this, a

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

• ]. Such activation has enabled a wide array of transformations, including metal-catalyzed cross-couplings via oxidative addition into the amide C–N bond (Scheme 1c) [32][33][34][35][36], and transition-metal-free acyl substitutions facilitated by improved leaving-group ability [37][38][39][40]. Although

• secondary and tertiary amides with octanol catalyzed by CeO2, utilizing the advantage of its cooperative acid–base functionalities (Scheme 2) [46]. Under the optimized conditions, N,N-dimethylbenzamide (3) and N,N-diethylbenzamide (4) were smoothly converted to octyl benzoate (1) in 93% and 95% yield

• intermediate E, the carboxylic acid is formed, regenerating the acidic and basic surface sites of the Nb2O5 catalyst. In 2020, Mashima et al. reported an intriguing accelerating effect of potassium alkoxides on the manganese-catalyzed esterification of tertiary amides (Scheme 4) [48]. They found that potassium

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

• ]. In 2018, Kota and Sreevani prepared spirobarbiturates via a Mo(CO)6-catalyzed intermolecular [2 + 2 + 2] cycloaddition of propargyl halides with dipropargylbarbituric acid [24]. Almeida and colleagues described the formation of spiroindoline barbiturates via thermal rearrangement of 2,1-benzisoxazole

Arene activation via π-bond localization: concepts and opportunities

• Paul Meiners,
• Julian J. Melder and
• Tobias Morack

Beilstein J. Org. Chem. 2026, 22, 257–273, doi:10.3762/bjoc.22.19

• disrupting the aromatic core, such as electrophilic and nucleophilic aromatic substitutions, transition metal-catalyzed cross-couplings [11], and C–H functionalizations [12]. Taken together with their natural abundance, these transformations have established arenes and heteroarenes as versatile synthetic

• sequence elegantly illustrates how η4-coordination can orchestrate multistep bond construction. Finally, η4-bound intermediates have been proposed as intermediates in catalytic transformations – most notably in Chirik’s molybdenum-catalyzed arene hydrogenations [106][107] – highlighting the emerging

A mild and atom-efficient four-component cascade strategy for the construction of biologically relevant 4-hydroxyquinolin-2(1H)-one derivatives

• Dmitrii A. Grishin,
• Kseniia I. Sharkovskaia,
• Ilya G. Kolmakov,
• Daria A. Ipatova,
• Rostislav A. Petrov,
• Nikolai D. Dagaev,
• Dmitry A. Skvortsov,
• Maria G. Khrenova,
• Valeriy V. Andreychev,
• Sergei A. Evteev,
• Yan A. Ivanenkov,
• Roman L. Antipin,
• Olga А. Dontsova and
• Elena K. Beloglazkina

Beilstein J. Org. Chem. 2026, 22, 244–256, doi:10.3762/bjoc.22.18

• reactions catalyzed by diverse agents (Scheme 1). For instance, in 2013, Shi et al. described a three-component reaction involving 4-hydroxyquinolin-2(1H)-one, an aromatic aldehyde, and Meldrum’s acid, catalyzed by ʟ-proline under heating [37]. In the same year, Kurosh Rad-Moghadam and co-workers developed

• a related protocol operating at room temperature using the ionic liquid [Bmim]HSO4 as a catalyst, expanding the scope to include aliphatic aldehydes [38]. Later, in 2017, Esmayeel Abbaspour-Gilandeh et al. reported a modified variant of this transformation under solvent-free heating, catalyzed by

• in the reaction mixture [44][45]. Previous studies have reported the synthesis of compounds structurally related to our targets – 4-aryl-4,6-dihydro-2H-pyrano[3,2-c]quinoline-2,5(3H)-diones – via multicomponent reactions catalyzed by various agents (Scheme 1) [37][38][39]. These one-pot reactions

Screwing the helical chirality through terminal peri-functionalization

• Devesh Chandra,
• Sachin and
• Upendra Sharma

Beilstein J. Org. Chem. 2026, 22, 205–212, doi:10.3762/bjoc.22.14

• catalysts [33]. A domino reaction was developed, beginning with a PPS L2-catalyzed Michael addition of phosphine oxides 7 to nitro-substituted oxa[5]helicenes 6, followed by a copper-promoted aromatization. This sequence efficiently produced phosphorus-containing oxa[5]helicene derivatives 8 in high yields

• corresponding amine followed by N-tosylation, providing product 10 in 63% yield without altering the enantiomeric excess (Scheme 4). Additionally, product 8g was converted into the chiral phosphine ligand 12 while fully preserving its helical chirality and successfully applied in palladium-catalyzed

• [5]helicenes. Scale-up synthesis and post-synthetic application of chiral helical product 8g. Post-synthetic transformation of product 8g to chiral phosphine ligand 12 and its application in Pd-catalyzed reactions. Acknowledgements The authors acknowledge the CSIR-IHBT, Palampur for providing

Base-promoted deacylation of 2-acetyl-2,5-dihydrothiophenes and their oxygen-mediated hydroxylation

• Vladimir G. Ilkin,
• Margarita Likhacheva,
• Igor V. Trushkov,
• Tetyana V. Beryozkina,
• Vera S. Berseneva,
• Vladimir T. Abaev,
• Wim Dehaen and
• Vasiliy A. Bakulev

Beilstein J. Org. Chem. 2026, 22, 192–204, doi:10.3762/bjoc.22.13

• oxidation of ketones includes C‒C-bond cleavage, and carboxylic acids are predominantly formed. This can be achieved by the treatment of acyclic ketones with hypohalites [13], in the nitroarene-catalyzed oxidation with oxygen under basic conditions [14] or by the use of hypervalent iodine compounds (Scheme

• available reagents is an important task. Recently, we have developed a copper(I)/rhodium(II)-catalyzed method toward two types of regioisomeric 2,5-dihydrothiophenes 1 and 4, containing an acetyl group [50]. In this work, to evaluate the synthetic utility of these compounds (the scope is presented at page

Highly electrophilic, gem- and spiro-activated trichloromethylnitrocyclopropanes: synthesis and structure

• Ilia A. Pilipenko,
• Mikhail V. Grigoriev,
• Olga Yu. Ozerova,
• Igor A. Litvinov,
• Darya V. Spiridonova,
• Aleksander V. Vasilyev and
• Sergey V. Makarenko

Beilstein J. Org. Chem. 2026, 22, 123–130, doi:10.3762/bjoc.22.5

• -Petersburg 199034, Russia 10.3762/bjoc.22.5 Abstract New highly electrophilic gem- and spiro-activated trichloromethylnitrocyclopropanes were obtained by the Michael-initiated ring closure (MIRC) reaction of 1-bromo-1-nitro-3,3,3-trichloropropene with linear and cyclic CH-acids catalyzed by bases

Total synthesis of natural products based on hydrogenation of aromatic rings

• Haoxiang Wu and
• Xiangbing Qi

Beilstein J. Org. Chem. 2026, 22, 88–122, doi:10.3762/bjoc.22.4

• in the presence of metal catalysts including Pd or Ir and different ligands. In 2021 and 2022, Wang and co-workers reported two impressive hydroboration–hydrogenation reactions catalyzed by FLP (triarylphenylborane) that reduced pyridine compounds 11 or 15 to dihydropyridine compounds 12 or chiral

• stereoselectively. In 2023, Chen in collaboration with Zhang, reported a simple and efficient rhodium–thiourea-catalyzed asymmetric hydrogenation reaction for the synthesis of highly optically pure tetrahydroquinoxaline 48 and dihydroquinoxalinones 50 (Scheme 6) [57]. Due to the mild conditions and broad substrate

• 53 while retaining the benzene ring structure using an iridium catalyst to selectively hydrogenate indoles and benzofurans (Scheme 7) [59]. The hydrogenated products were obtained in 90% yield with 98% ee on average. In 2024, Yin and co-workers reported an innovative palladium-catalyzed asymmetric

Advances in Zr-mediated radical transformations and applications to total synthesis

• Hiroshige Ogawa and
• Hugh Nakamura

Beilstein J. Org. Chem. 2026, 22, 71–87, doi:10.3762/bjoc.22.3

• Yamaguchi published a review on radical reactions catalyzed by zirconium complexes [6]. Their review provides a comprehensive summary, particularly of photo-redox reactions involving zirconium catalysis. In the present review, we focus on three aspects: 1) Zr-mediated stoichiometric radical reactions 2) Zr

• -catalyzed radical reactions 3) Applications of Zr-mediated reactions in total synthesis. To apply these reactions to total synthesis, high functional group compatibility is required. Thus, the insights gained here can be used to assess the potential of zirconium-catalyzed radical reactions. Review Zr

• summarized and described. In 2007, Oshima et al. reported the zirconocene-catalyzed alkylative dimerization of 2-methylene-1,3-dithiane (Scheme 3) [13]. When alkyl halide 13 was treated with Schwartz’s reagent in the presence of butylmagnesium bromide, the generation of an alkyl radical via XAT process and

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

• -catalyzed additions of alkynes to acyl chlorides to access β-chlorovinyl ketones (2024) [31]. A review by Sharma and Singh covers comprehensively the synthesis and application of β-halovinyl aldehydes [32]. It should be noted that the synthesis of β-chloroalkenes substituted with an electron-withdrawing

• group in the α-position (e.g., aldehyde, ketone, sulfone, nitro) is beyond the scope of this review. In 2011, Guinchard and Roulland reviewed Pd-catalyzed cross-couplings of 1,1-dichloroalkenes and boron-chlorination reactions in the context of natural product synthesis (Figure 3C) [33]. Takai’s

• -catalyzed C–halogen bond formation (Figure 3E) [36]. Exchange reactions were reviewed by Evano and Nitelet in 2018 (Figure 3F) [37]. In 2020, Gandelman and co-workers provided an overview of decarboxylative chlorination reactions of carboxylic acids (Figure 3G) [38]. Hoveyda’s 2023 review highlights

One-pot synthesis of ethylmaltol from maltol

• Immanuel Plangger,
• Marcel Jenny,
• Gregor Plangger and
• Thomas Magauer

Beilstein J. Org. Chem. 2025, 21, 2755–2760, doi:10.3762/bjoc.21.212

• from corncob to access pyromeconic acid [6]. The second group of synthetic strategies takes advantage of furfural (4), which originates from the acid-catalyzed dehydration of agricultural biomass. It is then converted with an ethyl Grignard compound to alcohol 5 [7]. From alcohol 5, oxidation state

Total synthesis of asperdinones B, C, D, E and terezine D

• Ravi Devarajappa and
• Stephen Hanessian

Beilstein J. Org. Chem. 2025, 21, 2730–2738, doi:10.3762/bjoc.21.210

• methods to prenyl- and allylindoles as starting points toward the synthesis of asperdinones B, C, D, and E (1–4) as well as to terezine D (6). To access 4-prenylindole, we adopted a Pd-catalyzed Suzuki coupling of 3,3-dimethyl-1-butene-3-pinacol boronate with bromoindoles [52]. Unfortunately, despite the

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

• ionic liquid- [16] or lactic acid-catalyzed [17] reactions of alkynoates, KSCN and water under ultrasound conditions as well as by the reactions of alkynoates, KSCN and water using deep eutectic solvents [18]. Reddy and co-workers [19] proposed an approach to thiocyano enones through the

• cyclization to isothiazolones (Scheme 1). Silver- [20] and gold-catalyzed [21] hydrothiocyanations of haloalkynes with thiocyanate salts in acetic acid to give Z-vinyl thiocyanates were reported. The reaction between alkynic hydrazones and KSCN in AcOH/MeCN delivered N-iminoisothiazolium ylides [22] (Scheme 1

Recent advancements in the synthesis of Veratrum alkaloids

• Morwenna Mögel,
• David Berger and
• Philipp Heretsch

Beilstein J. Org. Chem. 2025, 21, 2657–2693, doi:10.3762/bjoc.21.206

• enantiomeric excess of 92%. This asymmetric hydrogenation included a novel iridium catalyst featuring a chiral SpiroBAP (spiro bidentate aminophosphorane) ligand, which has been developed previously by this group and was now successfully applied in this synthesis [36]. A silver-catalyzed, enantioselective

• selectively, and, through acid-catalyzed cyclization, the spiro-E-ring was fused. Elimination of the alcohol moiety at C13 installed the double bond in the correct position at C12–C13. Final Fmoc-deprotection furnished cyclopamine (6). In summary, the Zhu/Gao group disclosed the total synthesis of cyclopamine

• material was concentrated and subjected to a Horner–Wadsworth–Emmons (HWE) reaction with phosphonate 77. In the same pot, the alkyne moiety was also methylated to furnish dienyne 72. Now, the key Diels–Alder step could be performed. Initial attempts failed, but a rhodium-catalyzed reaction in