(Bio)isosteres of ortho- and meta-substituted benzenes

• H. Erik Diepers and
• Johannes C. L. Walker

Beilstein J. Org. Chem. 2024, 20, 859–890, doi:10.3762/bjoc.20.78

• different related tri- and polysubstituted scaffolds have been synthesised in the last few years, with the aim of providing more saturated and three-dimensional molecules for drug discovery. While many of them have not been explicitly suggested as potential isosteres for variously substituted benzenes, they

Synthesis of new representatives of A₃B-type carboranylporphyrins based on meso-tetra(pentafluorophenyl)porphyrin transformations

• Victoria M. Alpatova,
• Evgeny G. Rys,
• Elena G. Kononova and
• Valentina A. Ol'shevskaya

Beilstein J. Org. Chem. 2024, 20, 767–776, doi:10.3762/bjoc.20.70

• meso-pentafluorophenyl-substituted porphyrins. Carboranes, due to their unique physical and chemical properties such as high chemical and biological stability [28][29], three-dimensional aromaticity [30][31], low toxicity [28], high hydrophobicity, and enriched boron content [32][33] are perspective

Entry to new spiroheterocycles via tandem Rh(II)-catalyzed O–H insertion/base-promoted cyclization involving diazoarylidene succinimides

• Alexander Yanovich,
• Anastasia Vepreva,
• Ksenia Malkova,
• Grigory Kantin and
• Dmitry Dar’in

Beilstein J. Org. Chem. 2024, 20, 561–569, doi:10.3762/bjoc.20.48

• modern drug design [1][2]. They are known to promote higher success rates, when targeting three-dimensional protein molecules [3][4]. Furthermore, a wide variety of spirocyclic fragments can be spotted in natural products [5]. The aspects mentioned unveil the development of synthetic methodologies

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

Elucidating the glycan-binding specificity and structure of Cucumis melo agglutinin, a new R-type lectin

• Jon Lundstrøm,
• Emilie Gillon,
• Valérie Chazalet,
• Nicole Kerekes,
• Antonio Di Maio,
• Ten Feizi,
• Yan Liu,
• Annabelle Varrot and
• Daniel Bojar

Beilstein J. Org. Chem. 2024, 20, 306–320, doi:10.3762/bjoc.20.31

• no binding to unsubstituted galactose, we rather hypothesized the existence of specific interactions made with the C2-substituents, that did not exist in other R-type lectins such as RCA1. To determine this, we set out to resolve the detailed three-dimensional structure of CMA1 via X-ray

Tying a knot between crown ethers and porphyrins

• Maksym Matviyishyn and
• Bartosz Szyszko

Beilstein J. Org. Chem. 2023, 19, 1630–1650, doi:10.3762/bjoc.19.120

• synthesis of three-dimensional cryptands by Lehn [5], and spherands by Cram [6]. Later on, various classes of macrocyclic compounds were designed, demonstrating remarkable features in areas spreading from simple coordination chemistry [7], through host–guest chemistry, sensing [8], biomedicine [9], and

• molecules, e.g., catenanes and rotaxanes (Figure 16C). The formation of such compounds would eventually result in the formation of a unique group of three-dimensional ligands with co-existing porphyrin-like and crown ether cavities. The perspective article has highlighted the wide range of crown ether

Cyclodextrins permeabilize DPPC liposome membranes: a focus on cholesterol content, cyclodextrin type, and concentration

• Ghenwa Nasr,
• Hélène Greige-Gerges,
• Sophie Fourmentin,
• Abdelhamid Elaissari and
• Nathalie Khreich

Beilstein J. Org. Chem. 2023, 19, 1570–1579, doi:10.3762/bjoc.19.115

• of the native CDs, their three-dimensional structure, and their dimensions (n = 6, 7, and 8 glucopyranose units for α-, β-, and γ-CD, respectively). This figure was reused by permission from Springer Nature from [21]. (“130 years of cyclodextrin discovery for health, food, agriculture, and the

Aromatic C–H bond functionalization through organocatalyzed asymmetric intermolecular aza-Friedel–Crafts reaction: a recent update

• Anup Biswas

Beilstein J. Org. Chem. 2023, 19, 956–981, doi:10.3762/bjoc.19.72

• the reaction partners in a highly ordered three dimensional transition state through noncovalent interactions (like H-bonding, π–π interactions) thus promoting the stereoselective reaction. Examples of covalent bonding organocatalysts are amines [6][7], N-heterocyclic carbenes [8][9], phosphines [10

• carbonyl oxygen of 69 in the ternary complex, thus bringing more rigidity in the three dimensional transition state (Scheme 18) [46]. In 2021, Chen and co-workers documented a chiral phosphoric acid P17-catalyzed aza-Friedel–Crafts process between racemic 2,3-dihydroisoxazol-3-ol derivatives 76 and

Construction of hexabenzocoronene-based chiral nanographenes

• Ranran Li,
• Di Wang,
• Shengtao Li and
• Peng An

Beilstein J. Org. Chem. 2023, 19, 736–751, doi:10.3762/bjoc.19.54

• glum of (P,P,M/M,M,P)-117 was measured as 2 × 10−4. Cyclooctatetraphenylene (COT-Ph) is a π-conjugated scaffold, whose three-dimensional (3D) geometry is based on its saddle shape. Martín and co-workers reported the 3D NG 121 by the introduction of four HBC units into COT-Ph [60]. As shown in Scheme 14

• = 1375 M−1 cm−1 at 573 nm at 430 nm) for enantiopure 125 was obtained. In 2019, Wang and co-workers reported the largest atomically precise three-dimensional conjugated chiral nanographene propeller 128, representing the largest three-dimensional conjugated polyaromatics everprepared using scalable

• exploit three-dimensional aesthetic structures. The continuously developed novel structures contented our interests and curiosity. To further tune the optoelectronic or photophysical properties of nanographenes for real applications, heteroatom doping was found to be an effective strategy. The

A novel spirocyclic scaffold accessed via tandem Claisen rearrangement/intramolecular oxa-Michael addition

• Anastasia Vepreva,
• Alexander Yanovich,
• Dmitry Dar’in,
• Grigory Kantin,
• Alexander Bunev and
• Mikhail Krasavin

Beilstein J. Org. Chem. 2022, 18, 1649–1655, doi:10.3762/bjoc.18.177

• higher success rates [2] in discovering new cases of affinity towards a three-dimensional protein molecule [3]. Spirocycles of all sorts are omnipresent in the natural product realm [4]. Among the approved medicines the following spirocyclic molecules are notable: spironolactone for heart disease and

Characterization of a new fusicoccane-type diterpene synthase and an associated P450 enzyme

• Jia-Hua Huang,
• Jian-Ming Lv,
• Liang-Yan Xiao,
• Qian Xu,
• Fu-Long Lin,
• Gao-Qian Wang,
• Guo-Dong Chen,
• Sheng-Ying Qin,
• Dan Hu and
• Hao Gao

Beilstein J. Org. Chem. 2022, 18, 1396–1402, doi:10.3762/bjoc.18.144

• might adopt a similar strategy as MgMS to initiate C2,6 cyclization though protonation at C2 by bulky water. To obtain further insights into the C2,6-cyclization process of TadA, its three-dimensional (3D) protein structure was constructed with SWISS-MODEL using PaFS (PDB entry 5er8) as the template

Cytochrome P450 monooxygenase-mediated tailoring of triterpenoids and steroids in plants

• Karan Malhotra and
• Jakob Franke

Beilstein J. Org. Chem. 2022, 18, 1289–1310, doi:10.3762/bjoc.18.135

• sterol scaffolds have drastically different three-dimensional shapes. For this reason, CYPs are typically specific to a certain group of triterpenoid scaffolds. Hence, we summarised our list of 149 triterpenoid/steroid CYPs (Table 1) according to their target scaffold. Figure 3 covers plant CYPs acting

Facile and diastereoselective arylation of the privileged 1,4-dihydroisoquinolin-3(2H)-one scaffold

• Dmitry Dar’in,
• Grigory Kantin,
• Alexander Bunev and
• Mikhail Krasavin

Beilstein J. Org. Chem. 2022, 18, 1070–1078, doi:10.3762/bjoc.18.109

• arylation product 9. The trans-diastereoselectivity in the latter process is reasonably justified by the approach of the arene molecule to carbocation 17 from the sterically less hindered side (Scheme 5). Compounds 9 have a pronounced three-dimensional character which makes this novel chemotype a promising

• -isoquinolone byproducts (formed exclusively in the absence of the arene). The extent of this side reaction was found to be dependent on the electronic character of the 1,4-DHIQs and the carbocation-intercepting arene molecule. Considering the pronounced three-dimensional character of 1,2,4-trisubstituted 1,4

Unusual highly diastereoselective Rh(II)-catalyzed dimerization of 3-diazo-2-arylidenesuccinimides provides access to a new dibenzazulene scaffold

• Anastasia Vepreva,
• Alexander S. Bunev,
• Andrey Yu. Kudinov,
• Grigory Kantin,
• Mikhail Krasavin and
• Dmitry Dar’in

Beilstein J. Org. Chem. 2022, 18, 533–538, doi:10.3762/bjoc.18.55

• diastereomer 2a is indicative of a sequence of concerted processes with an unambiguous stereochemistry control at each step where stereogenic centers are formed. Dibenzoazulenodipyrroles 2 have a pronounced three-dimensional character which make this chemotype promising as probe for protein–protein

Recent developments and trends in the iron- and cobalt-catalyzed Sonogashira reactions

• Surendran Amrutha,
• Sankaran Radhika and
• Gopinathan Anilkumar

Beilstein J. Org. Chem. 2022, 18, 262–285, doi:10.3762/bjoc.18.31

• ligand achieved the high activities of the Co-MS@MNPs/CS. Taking aryl halides and terminal alkynes as the reactants, Vajargahy and Dabiri discussed a facile method for a Sonogashira coupling reaction catalyzed by Pd/Co bimetallic nanoparticles supported on three-dimensional graphene (PdCoNPs-3DG) in

• aqueous medium under aerobic conditions (Scheme 26) [39]. The graphene support was prepared by oxidation of graphite, treatment of the resulting graphene oxide with ethylene diamine in an autoclave followed by freeze-drying to obtain three dimensional graphene with a high nitrogen content. Heating of the

Green synthesis of C5–C6-unsubstituted 1,4-DHP scaffolds using an efficient Ni–chitosan nanocatalyst under ultrasonic conditions

• Soumyadip Basu,
• Sauvik Chatterjee,
• Suman Ray,
• Suvendu Maity,
• Prasanta Ghosh,
• Asim Bhaumik and
• Chhanda Mukhopadhyay

Beilstein J. Org. Chem. 2022, 18, 133–142, doi:10.3762/bjoc.18.14

• transition metal ions due to the presence of abundant amino and alcohol groups in the structure [18]. Because of this chelating character, as well as due to the hydrophilicity, unique three-dimensional structure, and mechanical properties, chitosan has several catalytic applications [19][20]. In this work

Peptide stapling by late-stage Suzuki–Miyaura cross-coupling

• Hendrik Gruß,
• Rebecca C. Feiner,
• Ridhiwan Mseya,
• David C. Schröder,
• Michał Jewgiński,
• Kristian M. Müller,
• Rafał Latajka,
• Antoine Marion and
• Norbert Sewald

Beilstein J. Org. Chem. 2022, 18, 1–12, doi:10.3762/bjoc.18.1

• -dimensional space of PC1-3 led to 32 and 38 structural clusters for the cis and trans isomers, respectively. The first three representative structures are depicted in Figure 4, the first six clusters are projected in the three-dimensional space of PC1-3, and the corresponding representative structures are

• higher probability of occurrence (17.8%). The non-helical conformation c3 of P5 trans (7.5%) is slightly less populated than the corresponding c2 of P5 cis. The macrocycle of both isomers is found to be rather flexible, forming well-separated conformational clusters in the three-dimensional space of PC1

• simulations. The middle panel shows the three-dimensional projection of the six main PCA-based conformational clusters in the space of the first three principal components (PC). The lower panel presents a two-dimensional projection in the plane of the first two PCs. Each point corresponds to a trajectory

Cryogels: recent applications in 3D-bioprinting, injectable cryogels, drug delivery, and wound healing

• Luke O. Jones,
• Leah Williams,
• Tasmin Boam,
• Martin Kalmet,
• Chidubem Oguike and
• Fiona L. Hatton

Beilstein J. Org. Chem. 2021, 17, 2553–2569, doi:10.3762/bjoc.17.171

• alter cryogel pore size and mechanical properties. In addition, Tam et al. demonstrated the optical transparency with three-dimensional spatial control of immobilised bioactive growth factors using multiphoton patterning and cellular response to immobilised ligands as shown in Figure 6 [94]. Researchers

An initiator- and catalyst-free hydrogel coating process for 3D printed medical-grade poly(ε-caprolactone)

• Jochen Löblein,
• Thomas Lorson,
• Miriam Komma,
• Tobias Kielholz,
• Maike Windbergs,
• Paul D. Dalton and
• Robert Luxenhofer

Beilstein J. Org. Chem. 2021, 17, 2095–2101, doi:10.3762/bjoc.17.136

• ; surface modification; Introduction Additive manufacturing, commonly referred to as three-dimensional (3D) printing, is an approach to create physical objects using layer-by-layer [1] or voxel-by-voxel fabrication [2]. 3D printed materials can be used for a broad spectrum of applications, including

Progress and challenges in the synthesis of sequence controlled polysaccharides

• Giulio Fittolani,
• Theodore Tyrikos-Ergas,
• Denisa Vargová,
• Manishkumar A. Chaube and
• Martina Delbianco

Beilstein J. Org. Chem. 2021, 17, 1981–2025, doi:10.3762/bjoc.17.129

Breaking paracyclophane: the unexpected formation of non-symmetric disubstituted nitro[2.2]metaparacyclophanes

• Suraj Patel,
• Tyson N. Dais,
• Paul G. Plieger and
• Gareth J. Rowlands

Beilstein J. Org. Chem. 2021, 17, 1518–1526, doi:10.3762/bjoc.17.109

• chains at non-adjacent carbon positions. Their constrained three-dimensional shapes enforce unusual conformations and interactions between the aromatic decks, all of which results in their unique properties [2][3][4][5]. The most studied cyclophane is [2.2]paracyclophane (1, Figure 1). Not only is it the

Photoinduced post-modification of graphitic carbon nitride-embedded hydrogels: synthesis of 'hydrophobic hydrogels' and pore substructuring

• Cansu Esen and
• Baris Kumru

Beilstein J. Org. Chem. 2021, 17, 1323–1334, doi:10.3762/bjoc.17.92

• results confirm the photoinduced polymerization within the hydrogel network. Visible light irradiation leads to a polymerization of monomers within the three‐dimensional hydrogel network, thus one can expect altered pore morphologies. In that regard, SEM images are useful to explore the pore

Structural effects of meso-halogenation on porphyrins

• Keith J. Flanagan,
• Maximilian Paradiz Dominguez,
• Zoi Melissari,
• Hans-Georg Eckhardt,
• René M. Williams,
• Dáire Gibbons,
• Caroline Prior,
• Gemma M. Locke,
• Alina Meindl,
• Aoife A. Ryan and
• Mathias O. Senge

Beilstein J. Org. Chem. 2021, 17, 1149–1170, doi:10.3762/bjoc.17.88

• ][12][13]. Such complexes have been reported for potential application in materials sciences (e.g., molecular sieves) as they form a three-dimensional lattice where more than 50% of the crystal capacity consists of open straight channels [5][6]. Noteworthy, Titi et al. reported that a chiral

Biochemistry of fluoroprolines: the prospect of making fluorine a bioelement

• Vladimir Kubyshkin,
• Rebecca Davis and
• Nediljko Budisa

Beilstein J. Org. Chem. 2021, 17, 439–460, doi:10.3762/bjoc.17.40

• elucidate three-dimensional structures of proteins. However, the substitution of proline by one of the remaining 19 coded amino acids can be harmful to protein folding and the functional properties. This is usually explained by the absence of the amide hydrogen atom and the cyclic nature of the proline ring

¹⁹F NMR as a tool in chemical biology

• Diana Gimenez,
• Aoife Phelan,
• Cormac D. Murphy and
• Steven L. Cobb

Beilstein J. Org. Chem. 2021, 17, 293–318, doi:10.3762/bjoc.17.28

• of which were consistent with those obtained in previous work but measured in cell membrane extracts [46]. Structural analysis of macromolecules using 19F NMR The three-dimensional (3D) structure of biomacromolecules and their conformational dynamics are often the starting point for the development