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Search for "intramolecular" in Full Text gives 1334 result(s) in Beilstein Journal of Organic Chemistry. Showing first 200.

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

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  • . A tentative mechanism that may be plausible is shown in Supporting Information File 1, Figure S21, which consists of (1) the nucleophilic attack of methylenetriphenylphosphorane to the exo-methylene group of 3, (2) the intramolecular carbon–carbon-bond formation at the carbonyl group, and (3) the
  • group (Figure S20, Supporting Information File 1), which will be due to the disrupted nucleophilic attack to the carbonyl group by the intramolecular steric repulsion toward the Bürgi–Dunitz angle. However, alternative mechanisms initiated by a conventional oxaphosphetane formation cannot not yet be
  • temperature-dependent 1H NMR measurements. The relatively preferable formation of bathtub conformation is attributable to the destabilization of the figure-eight structures by the intramolecular steric repulsion between the exo-methylene units and neighboring benzene rings. Resolution The resolution of rac-3
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Published 14 Jul 2025

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

Graphical Abstract
  • nm) attributed to reversible intramolecular charge transfer [20]. In parallel, several groups explored the functional versatility of heterohelicenes in device-oriented and sensing applications. Crassous’s group synthesized bipyridine-embedded helicenes via the Mallory reaction, enabling coordination
  • intramolecular Scholl reactions [24] (Table 3). All compounds exhibited strong absorption in the UV–vis region (250–450 nm) and fluorescence emission between 400–550 nm. Among these, compound 11c, a saddle-shaped dibenzodiaza[8]circulene, was particularly noteworthy as the first example of its kind synthesized
  • | values of approximately 3.0 × 10−3, offering new architectures for CPL-active helicenes [40]. Singh’s group developed fluorophore-conjugated aza[7]helicenes 27a–d, with 27b demonstrating pronounced intramolecular charge transfer (ICT), a high ΦF of 0.71 and an extended fluorescence lifetime (τ) of 15.5
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Published 11 Jul 2025

Tautomerism and switching in 7-hydroxy-8-(azophenyl)quinoline and similar compounds

  • Lidia Zaharieva,
  • Vera Deneva,
  • Fadhil S. Kamounah,
  • Nikolay Vassilev,
  • Ivan Angelov,
  • Michael Pittelkow and
  • Liudmil Antonov

Beilstein J. Org. Chem. 2025, 21, 1404–1421, doi:10.3762/bjoc.21.105

Graphical Abstract
  • molecules good candidates for molecular switches [50]. Recently, we have developed a series of 7-hydroxyquinoline Schiff bases, where the tautomeric proton transfer causes intramolecular twisting upon irradiation [51]. The process happens in the excited state and the competition between proton transfer and
  • intramolecular hydrogen bonding, keep planarity. However, this situation means that changes in their molar fractions cannot be detected by use of UV–vis spectroscopy, i.e. the tautomerism could be considered only in the frame of change between E and (KE+KK). In the spectra, shown in Figure 2, two distinct
  • group surrounded by fluorine atoms, which could spontaneously deprotonate in polar solvents, while the tautomeric OH/NH group is always a part of strong intramolecular hydrogen bonding and the possibility for deprotonation is low. The deprotonation of the phenyl OH group is also supposed by the
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Published 10 Jul 2025

N-Salicyl-amino acid derivatives with antiparasitic activity from Pseudomonas sp. UIAU-6B

  • Joy E. Rajakulendran,
  • Emmanuel Tope Oluwabusola,
  • Michela Cerone,
  • Terry K. Smith,
  • Olusoji O. Adebisi,
  • Adefolalu Adedotun,
  • Gagan Preet,
  • Sylvia Soldatou,
  • Hai Deng,
  • Rainer Ebel and
  • Marcel Jaspars

Beilstein J. Org. Chem. 2025, 21, 1388–1396, doi:10.3762/bjoc.21.103

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  • ]. The biosynthetic route of compound 1 leads to the amide-bond formation step between the PmsG-tethered threonine and salicylic acyl group leading to intramolecular dehydration. The decarboxylated product of histidine, histamine serves as a nucleophilic substrate to release the corresponding uncyclised
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Published 04 Jul 2025

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

Graphical Abstract
  • discussed in more detail and illustrated by specific examples. 1.1 C–O bond-forming cyclisations 1.1.1 Intramolecular Williamson etherifications: Discovered by Alexander Williamson in 1850, this reaction is an SN2 substitution in which a leaving group, typically a halide or sulphonate ester, is displaced by
  • of the resulting alkene [36]. In addition, this intramolecular etherification corresponds to the 4-exo-tet cyclisation which, in terms of kinetics, is the least favoured n-exo-tet cyclisation mode where n ≤ 7 [37]. Nevertheless, the Williamson etherification still remains one of the most common
  • oxidation of the metal centre turns the cobalt into an excellent leaving group, allowing for an intramolecular displacement reaction that affords the oxetane ring and regenerates the Co(II) catalyst. In 2023, Silvi et al. described a versatile and practical methodology that couples Williamson etherification
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Published 27 Jun 2025

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

Graphical Abstract
  • . When introducing electron-donating groups to address this contradiction, another vital impact arises, the intramolecular HAT would take place. The amidyl radical would abstract a hydrogen atom from the nearest C–H, i.e., 1,2-HAT. Taken all these together, the substituent group should be decently
  • 8, 9, and 10 with 59%, 60%, and 69% yields. This powerful and efficient toolkit effectively overcame the limitations of intramolecular HAT processes. Building on this strategy, Kanai’s group reported a novel HAT method employing a new radical precursor in an oxidative photocatalytic system in 2018
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Published 27 Jun 2025

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

Graphical Abstract
  • of an azulene-embedded nanographene 49, featuring embedded contiguous azulene units and a narrowed cove-type edge (Scheme 7) [49]. Compound 46 was first subjected to intramolecular oxidation using light-promoted DDQ and as the result the first azulene subunit was introduced giving PAH 47 in an
  • [52]. With the appropriate choice of substrates, this approach can also be used for the synthesis of π-extended azulenes. For example, Tobe and co-workers conducted the intramolecular cyclization of 1,4,5,8-tetrakis(mesitylethynyl)naphthalene 50 using I2 in CH2Cl2 (Scheme 8) [53]. In the reaction
  • resulted in the mixture of isomeric π-extended azulenes 51 and 52 in rather moderate yields of 8% and 8%, respectively. Both PAHs 51 and 52 contain also embedded non-alternant indenophenalene subunits. Similarly, Murakami and co-workers reported intramolecular dimerization of alkynes followed by a phenyl
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Published 26 Jun 2025

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

Graphical Abstract
  • rapid construction of complex molecular architectures. This review aims to summarize the diverse strategies for inducing intramolecular transformations of N-arylacrylamides using various carbon radical reagents, including methods initiated by photonic, thermal, or electrochemical processes, which have
  • been extensively investigated by researchers. Keywords: carbon radical reagents; intramolecular transformations; N-arylacrylamides; oxidative difunctionalization; radical reactions; Introduction Alkenes, as abundant and versatile feedstocks, have been widely employed in organic synthesis
  • , heteroarylmethanes, phenylethane, and cumene proved compatible with the reaction conditions, providing oxindoles 3a–k with yields ranging from 67% to 86%. As illustrated in Scheme 2, an iron-catalyzed difunctionalization of alkenes involved in intramolecular transformations involving a C(sp3)–H bond adjacent to a
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Published 24 Jun 2025

Enhancing chemical synthesis planning: automated quantum mechanics-based regioselectivity prediction for C–H activation with directing groups

  • Julius Seumer,
  • Nicolai Ree and
  • Jan H. Jensen

Beilstein J. Org. Chem. 2025, 21, 1171–1182, doi:10.3762/bjoc.21.94

Graphical Abstract
  • Chen et al. [4]. We are excluding cyclization reactions for which the regioselectivity is not only determined by the activation energy to form the palladacycle intermediate but also by which site is accessible for the intramolecular cyclization. Using the previously described workflow, we were able to
  • with the experimentally observed reaction site in green and the predicted reaction site marked by a blue circle. For molecule 1, we can see in the original paper from Yeung et al. [26] that the reaction preceding the C–H activation is an intramolecular cyclization between the C atom marked in green and
  • the C atom marked by a blue circle. This reaction was originally not labelled as a cyclization reaction, which is why we did not remove it from the dataset. Nevertheless, upon inspection, our QM workflow correctly predicts the reaction site(s) of the intramolecular cyclization as it predicts one of
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Published 16 Jun 2025

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

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  • Ashutosh Nath John Mark Awad Wei Zhang Department of Chemistry, University of Massachusetts Boston, 100 Morrissey Boulevard, Boston, MA 02125, USA 10.3762/bjoc.21.92 Abstract A new synthetic route initiated with Groebke–Blackburn–Bienaymé (GBB) followed by N-acylation, intramolecular Diels–Alder
  • –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
  • as HIV inhibitors [14]. The imidazo[1,2-a]pyridine ring can be readily synthesized by the GBB reaction [10][15], while the isoquinolinone ring is commonly generated by a cyclative lactamization process. Performing a GBB reaction followed by an intramolecular amidation is a good approach for making
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Published 13 Jun 2025

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

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Published 28 May 2025

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

Graphical Abstract
  • , lycopodine features a characteristic tetracyclic structure with a bridged cyclohexanone. To address the challenges associated with constructing the complex ring systems of this structure, She and co-workers devised an intramolecular aza-Prins cyclization strategy to form both the bridge ring and the N-hetero
  • the terminal alkene and the conformational strain of forming a bridge[3.2.1]bicycle might be responsible for a selective 6-exo-trig cyclization. From tricyclic compound 4, anti-Markovnikov oxidation catalyzed by palladium led to the formation of aldehyde 5. When treated with p-TsOH, the intramolecular
  • ring was then constructed via an intramolecular reductive Heck reaction from vinyl bromide 10 with exclusive regioselectivity. Considering the strain of forming the 7-membered ring, this highly efficient 7-endo-trig (vs 6-exo-trig) transannular Heck cyclization reaction was remarkable to be realized in
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Published 22 May 2025

Harnessing tethered nitreniums for diastereoselective amino-sulfonoxylation of alkenes

  • Shyam Sathyamoorthi,
  • Appasaheb K. Nirpal,
  • Dnyaneshwar A. Gorve and
  • Steven P. Kelley

Beilstein J. Org. Chem. 2025, 21, 947–954, doi:10.3762/bjoc.21.78

Graphical Abstract
  • expect this metal-free protocol for alkene amino-oxygenation to find widespread use in both academic and industrial synthetic chemistry. Poor performers. Existing reports of intramolecular alkene functionalization reactions with nitreniums have focused on amino-trifluoroacetoxylations. We show the first
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Published 19 May 2025

A convergent synthetic approach to the tetracyclic core framework of khayanolide-type limonoids

  • Zhiyang Zhang,
  • Jialei Hu,
  • Hanfeng Ding,
  • Li Zhang and
  • Peirong Rao

Beilstein J. Org. Chem. 2025, 21, 926–934, doi:10.3762/bjoc.21.75

Graphical Abstract
  • molecules could be synthesized from diol 9 through a late-stage modification involving adjustment of the oxidation state and regioselective acylation. The formation of 9 was envisioned to proceed via an intramolecular pinacol coupling [30][31] of [5,5,6,6]-tetracycle 10, which forges the A2 ring while
  • essential tertiary alcohol at C1. The β-hydroxylactone moiety (D ring) in 11 could be introduced through an intramolecular aldol condensation [35] of acetate 12. Ultimately, the preparation of 12 could be traced back to aldehyde 14 through 1,2-Grignard addition with an organomagnesium reagent [36] prepared
  • % brsm). Since the newly created configuration at C30 was inconsequential, an intramolecular aldol reaction was directly carried out by treatment with LiHMDS to furnish β-hydroxylactone, which could be converted to dienone 11 through TPAP oxidation. Having secured 11, we proceeded to evaluate the pivotal
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Published 12 May 2025

Silver(I) triflate-catalyzed post-Ugi synthesis of pyrazolodiazepines

  • Muhammad Hasan,
  • Anatoly A. Peshkov,
  • Syed Anis Ali Shah,
  • Andrey Belyaev,
  • Chang-Keun Lim,
  • Shunyi Wang and
  • Vsevolod A. Peshkov

Beilstein J. Org. Chem. 2025, 21, 915–925, doi:10.3762/bjoc.21.74

Graphical Abstract
  • isocyanides, followed by a silver(I) triflate-catalyzed intramolecular heteroannulation of the resulting pyrazole-tethered propargylamides occurring in a 7-endo-dig fashion. The approach is scalable and tolerates a diverse range of substitution patterns. Keywords: heterocycles; post-MCR transformations
  • intramolecular condensation with the arylglyoxal-derived keto-carbonyl group [37]. In 2024, the same group streamlined this strategy by utilizing unprotected anthranilic acids, enabling the assembly of benzo[e][1,4]diazepines 6 directly during the Ugi reaction step [38]. In 2013, Van der Eycken and co-workers
  • ][44] and hydroalkoxylations [45]. In 2013, Van der Eycken and co-workers described an intramolecular cationic gold-catalyzed post-Ugi heteroannulation of imidazoles with activated alkynes for the diversity-oriented synthesis of imidazo[1,4]diazepines 13 from Ugi-derived propargylamides 12 (Scheme 1c
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Published 08 May 2025

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

Graphical Abstract
  • in steering catalytic selectivity. In 2016, the Jiang group achieved regioselective control in the gold-catalyzed intramolecular hydroarylation of alkynes by modulating the electronic and steric effects of ligands (Scheme 2) [20]. Mechanistically, the electron-deficient phosphite ligand L1 and the
  • undergoes intramolecular cyclization into a proximal C(sp2)–H bond (ΔG‡ = +19.7 kcal·mol−1) to form Int-46, which reacts with 4-MePhSH (ΔG‡ = +14.9 kcal·mol−1) to yield radical intermediate Int-47 and a thiyl radical (4-MePhS·). Sequential thiol-assisted hydrogen shifts produce Int-48, followed by
  • -methylacryloylbenzamides, and 2-iodobiphenyls – thereby selectively synthesizing silacyclic compounds with varying ring sizes, including ten-membered, seven-membered, and five-membered rings. Mechanism (Scheme 15): Substrate 53 undergoes oxidative addition with Pd(0), followed by intramolecular carbopalladation to form
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Published 07 May 2025

Cu–Bpin-mediated dimerization of 4,4-dichloro-2-butenoic acid derivatives enables the synthesis of densely functionalized cyclopropanes

  • Patricia Gómez-Roibás,
  • Andrea Chaves-Pouso and
  • Martín Fañanás-Mastral

Beilstein J. Org. Chem. 2025, 21, 877–883, doi:10.3762/bjoc.21.71

Graphical Abstract
  • . Finally, the new enolate E evolves through intramolecular proton abstraction and elimination of boryllithium [20][21]. The formation of side product 3 observed when dichloromethane was used as a solvent could be explained by protonation of intermediate A, followed by transmetalation of the resulting
  • mechanism for the Cu-catalyzed dimerization of 4,4-dichoro-2-butenoic acid derivatives. a) KOt-Bu-mediated intramolecular cyclization of 9. b) Direct formation of cyclopropane 20 from gem-dichloride 5 using KOt-Bu as base. Optimization studies. Synthesis of densely functionalized (2,2-dichlorovinyl
  • )cyclopropanes by base-promoted intramolecular cyclization. Supporting Information Supporting Information File 2: Experimental procedures, characterization data and copies of NMR spectra. Funding Financial support from the AEI (PID2020-118237RB-I00), European Research Council (863914), Xunta de Galicia (ED431C
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Published 05 May 2025

Light-enabled intramolecular [2 + 2] cycloaddition via photoactivation of simple alkenylboronic esters

  • Lewis McGhie,
  • Hannah M. Kortman,
  • Jenna Rumpf,
  • Peter H. Seeberger and
  • John J. Molloy

Beilstein J. Org. Chem. 2025, 21, 854–863, doi:10.3762/bjoc.21.69

Graphical Abstract
  • , and control reactions support sensitization, enabling an intramolecular [2 + 2] cycloaddition to be realized accessing 3D bicyclic fragments containing a boron handle. Keywords: boron; catalysis; [2 + 2] cycloaddition; energy transfer; photochemistry; Introduction The strategic use of a photon to
  • . Herein, we demonstrate the sensitization of alkenylboronates to enable efficient intramolecular [2 + 2] cycloaddition using high energy photosensitizers (Figure 1C). Sensitization was quickly established and explored through the use of alkene scrambling (geometrical isomerization) reaction probes, to
  • generated triplet diradical in an intramolecular system. To further assess the properties relevant for intramolecular reactivity, substrate 3b was designed (see Supporting Information File 1 for full details), given that non-activated α,β-unsaturated systems are also comparatively underexplored via EnT
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Published 30 Apr 2025

4-(1-Methylamino)ethylidene-1,5-disubstituted pyrrolidine-2,3-diones: synthesis, anti-inflammatory effect and in silico approaches

  • Nguyen Tran Nguyen,
  • Vo Viet Dai,
  • Luc Van Meervelt,
  • Do Thi Thao and
  • Nguyen Minh Thong

Beilstein J. Org. Chem. 2025, 21, 817–829, doi:10.3762/bjoc.21.65

Graphical Abstract
  • forms 3a’–e’ will be attacked by methylamine (4) to yield the tetrahedral intermediate 6 and then, the intramolecular proton transfer will lead to intermediate 7. It has been proven that Schiff’ bases show normally higher reactivity than the corresponding carbonyl compounds towards nitrogen-containing
  • a dihedral angle of 49.86(10) 86.22(11)° with the phenyl rings C6–C11 and C18–C23, respectively. The angle between both phenyl rings is 70.76(11)°. The stereochemistry around the double bond is Z, allowing an intramolecular N–H···O hydrogen bond between one of the carbonyl oxygen atoms and the amino
  • ellipsoids at the 30% probability level. The intramolecular hydrogen bond is shown as red dashed line. The bioavailability radar of studied compounds 5a–e. The interactions of potential drugs 5a–c in the active site of enzyme iNOS. The interactions of potential drugs 5d and 5e and control drug (DEX) in the
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Published 24 Apr 2025

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

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  • phenyl rings' ortho, meta, or para positions. This method proceeded via an anodic oxidation, followed by intramolecular cyclization (Scheme 32). The key role of anodic oxidation became evident when the annulation product
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Published 16 Apr 2025

Development and mechanistic studies of calcium–BINOL phosphate-catalyzed hydrocyanation of hydrazones

  • Carola Tortora,
  • Christian A. Fischer,
  • Sascha Kohlbauer,
  • Alexandru Zamfir,
  • Gerd M. Ballmann,
  • Jürgen Pahl,
  • Sjoerd Harder and
  • Svetlana B. Tsogoeva

Beilstein J. Org. Chem. 2025, 21, 755–765, doi:10.3762/bjoc.21.59

Graphical Abstract
  • internal rotation in 11 via TS8 and reaction with TMSCN to give adduct 13 (see Figure 3). Distances and bond lengths are given in pm. Catalyst 7 is replaced in TS 11-12 by concerted electrophilic intramolecular substitution with formal trimethylsilyl cation as electrophile. Please note the surprisingly
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Published 14 Apr 2025

Synthesis of HBC fluorophores with an electrophilic handle for covalent attachment to Pepper RNA

  • Raphael Bereiter and
  • Ronald Micura

Beilstein J. Org. Chem. 2025, 21, 727–735, doi:10.3762/bjoc.21.56

Graphical Abstract
  • was impractical for the HBC derivative with a C4-handle (N-(4-bromobutyl)-HBC) due to intramolecular cyclization with the amine. To prevent intramolecular cyclization, we considered the 4-bromobutyl HBC ether 11 as a potential candidate with a 4-atom spacer. Accordingly, 4-hydroxybenzaldehyde was
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Published 04 Apr 2025

Origami with small molecules: exploiting the C–F bond as a conformational tool

  • Patrick Ryan,
  • Ramsha Iftikhar and
  • Luke Hunter

Beilstein J. Org. Chem. 2025, 21, 680–716, doi:10.3762/bjoc.21.54

Graphical Abstract
  • a potentially valuable tool for molecular design. Additional stabilisation of the gauche conformation of vicinal fluorohydrins can also be afforded by an intramolecular H-bond (II, Figure 8) [96][97][98]. Fluorine is a weaker H-bond acceptor than oxygen or nitrogen [99][100][101], but F···H
  • attraction can still be significant in some contexts [102][103] and the intramolecular H-bond depicted in II (Figure 8) can have a significant impact upon the properties of vicinal fluorohydrins [97]. The possibility of intramolecular H-bonding in vicinal fluorohydrins has important consequences for the
  • molecules’ intermolecular interactions too. The intramolecular H-bond makes the hydroxy group a weaker intermolecular H-bond donor [104] (e.g., 55 vs 54, Figure 8). This runs counter to a longstanding assumption [105] that the inductive effect of fluorine should always make the hydroxy group a stronger H
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Published 02 Apr 2025

Entry to 2-aminoprolines via electrochemical decarboxylative amidation of N‑acetylamino malonic acid monoesters

  • Olesja Koleda,
  • Janis Sadauskis,
  • Darja Antonenko,
  • Edvards Janis Treijs,
  • Raivis Davis Steberis and
  • Edgars Suna

Beilstein J. Org. Chem. 2025, 21, 630–638, doi:10.3762/bjoc.21.50

Graphical Abstract
  • 10.3762/bjoc.21.50 Abstract The electrochemical synthesis of 2-aminoprolines based on anodic decarboxylation–intramolecular amidation of readily available N-acetylamino malonic acid monoesters is reported. The decarboxylative amidation under Hofer–Moest reaction conditions proceeds in an undivided cell
  • [7][8] (Figure 2, reactions 1 and 2, respectively). Results and Discussion N-Acetylamino malonic acid monoester 9a possessing a tosyl-protected tethered amine was selected as a model substrate for the development of the intramolecular amidation under Hofer–Moest conditions. The acid 9a was prepared
  • initial deprotonation of carboxylic acid 9a by cathodically generated hydroxide is followed by anodic oxidation/decarboxylation of the formed carboxylate 9a-I to generate stabilized cation 9a-II. The latter undergoes intramolecular cyclization with the tethered N-nucleophile into cyclic aminal 6a. In a
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Published 19 Mar 2025

Total synthesis of (±)-simonsol C using dearomatization as key reaction under acidic conditions

  • Xiao-Yang Bi,
  • Xiao-Shuai Yang,
  • Shan-Shan Chen,
  • Jia-Jun Sui,
  • Zhao-Nan Cai,
  • Yong-Ming Chuan and
  • Hong-Bo Qin

Beilstein J. Org. Chem. 2025, 21, 601–606, doi:10.3762/bjoc.21.47

Graphical Abstract
  • simonsol C, two reports have utilized alkaline dearomatization strategies and another report used an intramolecular Heck reaction as the key reaction [5][6][7]. However, there have been no reports or studies utilizing acidic dearomatization, which is also effective, to synthesize an arylated quaternary
  • carbon center. In the first report on the total synthesis of simonsol C (Scheme 1), in 2016 Banwell’s group employed an intramolecular Heck reaction as key step to furnish the aryl-containing quaternary center and simultaneously construct the benzofuran skeleton [7]. This synthesis involved a total of 12
  • scaffold of simonsol C, utilizing an alkaline dearomatization as the key reaction, followed by a functional-group-selective Wittig reaction and concurrent oxy-Michael addition [6]. A bromophenol acetal was used in the intramolecular alkylative dearomatization, which was first reported by Magnus et al. [8
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Published 17 Mar 2025
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