Asymmetric organocatalyzed synthesis of coumarin derivatives

• Natália M. Moreira,
• Lorena S. R. Martelli and
• Arlene G. Corrêa

Beilstein J. Org. Chem. 2021, 17, 1952–1980, doi:10.3762/bjoc.17.128

• amines enables both the formation of an imine ion with the enone and activation of the hydroxycoumarin by hydrogen bonding [41]. Despite the long reaction time (3 days), the desired products 3 were obtained with good to excellent yields and moderate enantiomeric excesses (Scheme 9). A new organocatalyst

• proposed transition state includes activations of the enone via an iminium ion and the coumarin by hydrogen bonding. A series of optically active polycyclic pyranocoumarin derivatives 37 was obtained in high yields with excellent enantioselectivities (up to 97% ee) (Scheme 12). Kowalczyk and Albrecht

• discussed above, the organocatalysts may also proceed by noncovalent activation, in which a hydrogen bond or an ion pair is formed. A broad variety of mono- and bifunctional chiral hydrogen-bonding organocatalysts has been developed, in special using cinchona alkaloid derivatives [52]. In this sense, Lin

Cationic oligonucleotide derivatives and conjugates: A favorable approach for enhanced DNA and RNA targeting oligonucleotides

• Mathias B. Danielsen and
• Jesper Wengel

Beilstein J. Org. Chem. 2021, 17, 1828–1848, doi:10.3762/bjoc.17.125

• latter strategy can be divided into the conjugation of amine groups onto ONs still attached to the solid support, or onto ONs in solution after cleavage from the solid support. The C-5 position of the pyrimidine ring has in general been the most used attachment point since it is not involved in hydrogen

• bonding and is facing the major groove upon duplex formation [27]. An illustrative approach that allowed the exploration of the 5-position of the pyrimidine ring as attachment site involved the use of 5-methoxycarbonylmethyl-2'-deoxyuridine and 5-trifluoroethoxycarbonyl-2’-deoxycytidine building blocks in

Development of N-F fluorinating agents and their fluorinations: Historical perspective

• Teruo Umemoto,
• Yuhao Yang and
• Gerald B. Hammond

Beilstein J. Org. Chem. 2021, 17, 1752–1813, doi:10.3762/bjoc.17.123

• shown in Scheme 40, the 18-2 pyridinium series proved to be effective fluorinating agents for a wide range of substrates. Moreover, an extremely high ortho-selectivity was observed in the fluorination of phenol. This could be attributed to a hydrogen-bonding interaction between the sulfonate anion and

Chemical approaches to discover the full potential of peptide nucleic acids in biomedical applications

• Nikita Brodyagin,
• Martins Katkevics,
• Venubabu Kotikam,
• Christopher A. Ryan and
• Eriks Rozners

Beilstein J. Org. Chem. 2021, 17, 1641–1688, doi:10.3762/bjoc.17.116

• and diagnostics that depend on Watson–Crick hydrogen bonding to natural nucleic acids. An unexpected discovery of early studies was that the triplex-forming PNAs built of pyrimidine monomers formed a 2:1 PNA–DNA–PNA strand-invasion triplex instead of the expected 1:1 PNA–dsDNA triplex (c.f., Figure 2A

• features [42]. The hydrogen bonding between PNA and RNA backbones is most likely the reason behind the >10-fold higher stability PNA–dsRNA triplexes [28][29][30][31] (compared to PNA–dsDNA) that favor structures having the ideal interphosphate distance of ≈6 Å. In contrast, the interphosphate distances in

• –C triplets than J when binding to dsRNA, which was suggested to be a combined effect of improved van der Waals contacts, base stacking, hydrogen bonding, and reduced dehydration energy [98]. Replacement of three Js with Ls increased the binding affinity of a PNA 8-mer ≈4-fold [98]. In addition, the

Chemical synthesis of C6-tetrazole ᴅ-mannose building blocks and access to a bioisostere of mannuronic acid 1-phosphate

• Eleni Dimitriou and
• Gavin J. Miller

Beilstein J. Org. Chem. 2021, 17, 1527–1532, doi:10.3762/bjoc.17.110

• has a similar pKa to a carboxylate yet provides enhanced hydrogen bonding capability and alternative prospects for permeability due to a larger hydrophobic region enabling improved lipophilic contacts. These alternative properties and a prospect for their inclusion within new alginate fragments led us

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

• the two aromatic rings as defined by carbon atoms 3–7 on the meta-ring and 12, 13, 15, 16 on the para-ring is 13.1° for [2.2]metaparacyclophane (3) [32], and 13.9° for the disubstituted derivative 5. The nitro group is held in the plane of the meta-ring by hydrogen bonding with the hydroxy group at C4

• . In the cyclohexadienone cyclophane 6, with its extra sp3-hybridized atom to the bridge, the distortion is reduced, the angle between the planes is just 7°. The conformation of the nitro group has changed. In the absence of a hydroxy group for hydrogen bonding, there is a repulsion between the nitro

Co-crystallization of an organic solid and a tetraaryladamantane at room temperature

• Fabian Rami,
• Jan Nowak,
• Felix Krupp,
• Wolfgang Frey and
• Clemens Richert

Beilstein J. Org. Chem. 2021, 17, 1476–1480, doi:10.3762/bjoc.17.103

• group. But again, hydrogen bonds between phenol hydroxy groups and the alkoxy substituent of the crystallization chaperone can be resolved. So, in both co-crystal lattices, hydrogen bonding stabilizes the packing arrangement. For TDA/phenol, the host builds the crystal lattice with TDA molecules in

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

• were characterized via FTIR analysis to elucidate structural footprints of CM embedding and vTA photographing. The broad peak in the range from 3639 cm−1 to 3136 cm−1 corresponds to the hydrogen bonding between carboxyl and hydroxy groups with amide functionality of the hydrogel backbone. Significant

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

• ‘guests’ within the crystal lattice, through hydrogen-bonding and van der Waals forces. Thereafter, research over the crystal engineering of porphyrins has focused on the noncovalent interactions, such as hydrogen bonds and halogen bonds, or metal coordination interactions [2][3][4][5][6][7][8][9][10][11

• architecture based on C–I···N and C–I···π interactions was formed through halogen bonding in the lattice of self-assembly of meso-tetraarylporphyrins [7]. In recent years there has been a strong uprising interest for substituting hydrogen-bonding motifs with their halogen-bonding counterparts. This is due to

• their relative versatility in areas such as directionality, the tunability of the σ-hole, hydrophobicity, and donor atom size [14]. These traits allow for the design of novel supramolecular architectures which are directive and reproducible, without relying on the hydrogen-bonding functionality which in

N-tert-Butanesulfinyl imines in the asymmetric synthesis of nitrogen-containing heterocycles

• Joseane A. Mendes,
• Paulo R. R. Costa,
• Miguel Yus,
• Francisco Foubelo and
• Camilla D. Buarque

Beilstein J. Org. Chem. 2021, 17, 1096–1140, doi:10.3762/bjoc.17.86

• arrangement of the sulfinyl group is the most stable conformation of the imine, due to the contribution of the hydrogen bonding of the oxygen and the iminic hydrogen. In this scenario, the tribromomethyl anion attacked the less hindered Re face of the imine with (RS) configuration (Scheme 6). The

Synthetic accesses to biguanide compounds

• Oleksandr Grytsai,
• Cyril Ronco and
• Rachid Benhida

Beilstein J. Org. Chem. 2021, 17, 1001–1040, doi:10.3762/bjoc.17.82

• structures to handle: their hydrogen-bonding and complexation properties complicate their isolation and purification, and the numerous tautomeric forms and partially exchangeable protons render the analysis sometimes tricky. Mostly, biguanides suffer from an evident lack of knowledge and efficient procedures

Application of the Meerwein reaction of 1,4-benzoquinone to a metal-free synthesis of benzofuropyridine analogues

• Rashmi Singh,
• Tomas Horsten,
• Rashmi Prakash,
• Swapan Dey and
• Wim Dehaen

Beilstein J. Org. Chem. 2021, 17, 977–982, doi:10.3762/bjoc.17.79

• dibenzofuran have been less explored, although they may have significant bioactivity. Introducing nitrogen to the dibenzofuran system is expected to increase the water solubility and potential bioavailability due to enhanced hydrogen bonding. Figure 2 presents a few examples of azadibenzofuran molecules. One

Beyond ribose and phosphate: Selected nucleic acid modifications for structure–function investigations and therapeutic applications

• Christopher Liczner,
• Kieran Duke,
• Gabrielle Juneau,
• Martin Egli and
• Christopher J. Wilds

Beilstein J. Org. Chem. 2021, 17, 908–931, doi:10.3762/bjoc.17.76

• modification disrupts both the phosphate backbone and hydrogen bonding of an adjacent base pair whereas (S)-GNA has a minimal influence on the structure of the duplex [54] (Figure 4). Moreover, incorporation of (S)-GNA residues in the seed region of the antisense strand of siRNA was observed to mitigate off

Synthesis of β-triazolylenones via metal-free desulfonylative alkylation of N-tosyl-1,2,3-triazoles

• Soumyaranjan Pati,
• Renata G. Almeida,
• Eufrânio N. da Silva Júnior and
• Irishi N. N. Namboothiri

Beilstein J. Org. Chem. 2021, 17, 762–770, doi:10.3762/bjoc.17.66

• can be explained by taking both hydrogen bonding and steric factors into consideration. In the solid as well as in the solution state, all the three above-mentioned 1,3-dicarbonyls exist in the enol form which are considerably stable and therefore undergo tosylation easily to form the corresponding O

• of dimedone (2d). Unlike cyclic 1,3-dicarbonyls, the acyclic 1,3-dicarbonyls possess intramolecular hydrogen bonding and are in rapid equilibrium with their keto-form. In polar solvents, the stability of the enol form is further decreased and, therefore, the keto-enol equilibrium lies more towards

[2 + 1] Cycloaddition reactions of fullerene C₆₀ based on diazo compounds

• Yuliya N. Biglova

Beilstein J. Org. Chem. 2021, 17, 630–670, doi:10.3762/bjoc.17.55

• synthetic route to conjugates of C60 with cinnamaldehyde 206 and with chalcone 207. The synthetic route to conjugate C60 with a 2-nitrocinnamyl group. The synthetic route to a C60 dimer connected through a highly directional fourfold hydrogen bonding motif. The synthetic route to quadruple hydrogen‐bonded

The synthesis of chiral β-naphthyl-β-sulfanyl ketones via enantioselective sulfa-Michael reaction in the presence of a bifunctional cinchona/sulfonamide organocatalyst

• Deniz Tözendemir and
• Cihangir Tanyeli

Beilstein J. Org. Chem. 2021, 17, 494–503, doi:10.3762/bjoc.17.43

• transition state model to explain the origin of the stereoinduction was proposed (Scheme 2), according to the Houk’s Brønsted acid hydrogen bonding model. Guo’s computational work in 2017 on the sulfa-Michael addition of thiols to enones in the presence of cinchona alkaloid-type organocatalysts showed that

Multiswitchable photoacid–hydroxyflavylium–polyelectrolyte nano-assemblies

• Alexander Zika and
• Franziska Gröhn

Beilstein J. Org. Chem. 2021, 17, 166–185, doi:10.3762/bjoc.17.17

• molecular recognition processes have been established based on different non-covalent interactions such as hydrogen bonding [9][10][11][12], π–π interaction [13][14][15][16][17], hydrophobic effects, and amphiphilicity [18][19][20][21]. It has been highly desirable to establish concepts that could be

• polyelectrolyte which can be altered through irradiation, the Flavy molecule may associate with the polyelectrolyte via hydrogen bonding and dipolar interaction, which will also respond to the pH value, either by a direct pH change or via the effect of the photoexcitation of the photoacid. To state the assembly

• pH 7 (Figure 8), the data reveal that the first and third binding site are exothermic with ΔH1 = −4.3 kJ/mol and ΔH3 = −172.7 kJ/mol per polyelectrolyte binding site, respectively, which shows that strong ionic interactions and hydrogen bonding constitute these binding processes. Probably these

Insight into functionalized-macrocycles-guided supramolecular photocatalysis

• Minzan Zuo,
• Krishnasamy Velmurugan,
• Kaiya Wang,
• Xueqi Tian and
• Xiao-Yu Hu

Beilstein J. Org. Chem. 2021, 17, 139–155, doi:10.3762/bjoc.17.15

• photocatalytic reaction with a rate acceleration facilitated by supramolecular host–guest interactions and hybrid materials are typically assisted by noncovalent forces, including Coulomb and van der Waals forces, hydrogen bonding, and π–π interactions. For potential supramolecular photocatalysts, they should

• of two different crown ether-substituted molecules, styrylbenzothiazole and cinnamic acid [18]. In this system, the Ba2+ cation can preorganize the two crown ether-substituted molecules into a supramolecular complex (Figure 2), which was further stabilized by hydrogen bonding and π–π interactions

Tuning the solid-state emission of liquid crystalline nitro-cyanostilbene by halogen bonding

• Subrata Nath,
• Alexander Kappelt,
• Matthias Spengler,
• Bibhisan Roy,
• Jens Voskuhl and
• Michael Giese

Beilstein J. Org. Chem. 2021, 17, 124–131, doi:10.3762/bjoc.17.13

• supramolecular liquid crystals, especially hydrogen bonding and halogen bonding have gained considerable attention [3][4][5][6][7]. In 2004, Bruce and co-workers reported the first example of a halogen-bonded liquid crystal based on pentafluoroiodobenzene and 4-alkoxystilbazole [5]. Ever since, several other

Supramolecular polymers with reversed viscosity/temperature profile for application in motor oils

• Jan-Erik Ostwaldt,
• Christoph Hirschhäuser,
• Stefan K. Maier,
• Carsten Schmuck and
• Jochen Niemeyer

Beilstein J. Org. Chem. 2021, 17, 105–114, doi:10.3762/bjoc.17.11

• constants, based on a sixfold hydrogen-bonding interaction, strengthened by coulombic interactions (see Figure 2a) [20][21]. The GCP motif has successfully been applied for the formation of supramolecular polymers in earlier works [22][23][24][25]. The ionic nature of the GCP motif allows self-pairing even

Circularly polarized luminescent systems fabricated by Tröger's base derivatives through two different strategies

• Cheng Qian,
• Yuan Chen,
• Qian Zhao,
• Ming Cheng,
• Chen Lin,
• Juli Jiang and
• Leyong Wang

Beilstein J. Org. Chem. 2021, 17, 52–57, doi:10.3762/bjoc.17.6

• the co-assembly strategy. The cogels show significant CPL emission and stoichiometry-controlled inversion of chirality due to the hydrogen bonding interactions and packing modes in the supramolecular co-assemblies. Owing to TB special V-shaped structure, rigid conformation, and nitrogen stereogenic

Molecular basis for protein–protein interactions

• Brandon Charles Seychell and
• Tobias Beck

Beilstein J. Org. Chem. 2021, 17, 1–10, doi:10.3762/bjoc.17.1

• discussed here can be employed to detect PPIs. Miura [41] and Carter et al. [11] provided a detailed explanation and comparison of such methodologies. Molecular interactions involved in PPIs There are different forces and mechanisms that affect PPIs and their formation, including hydrogen bonding [42][43

Synthesis of tetrafluorinated piperidines from nitrones via a visible-light-promoted annelation reaction

• Vyacheslav I. Supranovich,
• Igor A. Dmitriev and
• Alexander D. Dilman

Beilstein J. Org. Chem. 2020, 16, 3104–3108, doi:10.3762/bjoc.16.260

• modify basicity, lipophilicity, as well as the hydrogen-bonding properties of amines [4][5] makes fluorinated piperidines [6][7] attractive targets in medicinal chemistry [8][9]. Previous efforts were mainly focused on the synthesis of mono- and difluorinated compounds. A single fluorine atom is

Deoxyfluorination of acyl fluorides to trifluoromethyl compounds by FLUOLEAD^®/Olah’s reagent under solvent-free conditions

• Yumeng Liang,
• Akihito Taya,
• Zhengyu Zhao,
• Norimichi Saito and
• Norio Shibata

Beilstein J. Org. Chem. 2020, 16, 3052–3058, doi:10.3762/bjoc.16.254

• the products 2. A mechanism of the deoxyfluorination of the acyl fluorides with FLUOLEAD®/nHF·pyridine is proposed in Scheme 3. First, FLUOLEAD® is activated with (HF)n via hydrogen bonding to provide an activated form I, which induces a nucleophilic attack from the carbonyl oxygen of 1 to I providing

Chiral anion recognition using calix[4]arene-based ureido receptors in a 1,3-alternate conformation

• Tereza Horáčková,
• Jan Budka,
• Vaclav Eigner,
• Wen-Sheng Chung,
• Petra Cuřínová and
• Pavel Lhoták

Beilstein J. Org. Chem. 2020, 16, 2999–3007, doi:10.3762/bjoc.16.249

• Å, respectively. Every ureido group held one molecule of DMSO via synchronous hydrogen bonding interactions between the two NH protons and a sulfoxide oxygen atom (Figure 3a). The S=O···H–N distances were 1.995, 2.285, 2.033, and 2.328 Å, indicating strong interactions in the solid state. At the

• -acetylphenylalaninate. Design of chiral calix[4]arene-based receptors for anions. X-ray structure of 4a: (a) Top view into the cavity. (b) Side view of the same cavity. X-ray structure of 7a: (a) Hydrogen bonding interactions (black) in a dimeric motif, chalcogen interactions are shown in green. (b) π–π interactions in

• the dimeric motif. X-ray structure of 7d, showing hydrogen bonds between the ureido units (green) and hydrogen bonding of acetone molecules (black). One alkyl group in each calixarene was removed for better clarity. 1H NMR titration of 7c with N-acetyl-ᴅ-phenylalaninate and N-acetyl-ʟ-phenylalaninate