Glycosylation reactions mediated by hypervalent iodine: application to the synthesis of nucleosides and carbohydrates

• Yuichi Yoshimura,
• Hideaki Wakamatsu,
• Yoshihiro Natori,
• Yukako Saito and
• Noriaki Minakawa

Beilstein J. Org. Chem. 2018, 14, 1595–1618, doi:10.3762/bjoc.14.137

• have been widely used in organic synthesis [38]. Although originally used as oxidative agents, their use has spread to coupling reactions, including those for the formation of C–C bonds [39][40][41][42][43]. In the case of C–N bond formation, introduction of an azido group using PhI=O and TMSN3 was

• -mediated glycosylation led us to apply the reaction to the synthesis of carbocyclic nucleosides. In addition, we were also encouraged by the study of Ochiai, who developed the Friedel–Crafts reaction via umpolung of allylsilanes using hypervalent-iodine reagents [61] and the pioneering work on C–N bond

• developed. Since the Friedel–Crafts type reaction involved carbocation intermediate, the reaction always gave a mixture of products. Unfortunately, the reaction was not efficient. However, it is worthy that the oxidative coupling reaction contains a novel type of C–N bond formation and would help to

Hypervalent organoiodine compounds: from reagents to valuable building blocks in synthesis

• Gwendal Grelier,
• Benjamin Darses and
• Philippe Dauban

Beilstein J. Org. Chem. 2018, 14, 1508–1528, doi:10.3762/bjoc.14.128

• has led to a much lower yield when compared to that obtained from the corresponding diaryl-λ3-iodane. In 2011, the group of Detert has reported the first example of a palladium-catalyzed double C–N bond formation starting from the cyclic (phenyl)(pyrido)-λ3-iodane 61 (Scheme 25) [65]. The reaction

[3 + 2]-Cycloaddition reaction of sydnones with alkynes

• Veronika Hladíková,
• Jiří Váňa and
• Jiří Hanusek

Beilstein J. Org. Chem. 2018, 14, 1317–1348, doi:10.3762/bjoc.14.113

• formation followed by Cu–N dissociation and C–N bond formation. Experiments performed in t-BuOD/D2O [119] also showed almost exclusive (>98:2) deuteration of position 3 in the final pyrazole ring. This finding supports the idea of Cu(I)-acetylide addition to give 3-metalated pyrazole (Cu-pyrazolide) that is

Recent advances in synthetic approaches for medicinal chemistry of C-nucleosides

• Kartik Temburnikar and
• Katherine L. Seley-Radtke

Beilstein J. Org. Chem. 2018, 14, 772–785, doi:10.3762/bjoc.14.65

• glycosidic bond in 2'-deoxy ribonucleosides has a higher susceptibility to cleavage than in the corresponding ribonucleosides [38][39][40][41][43]. The rate of glycosidic (C–N) bond cleavage is enhanced by decreasing pH and enzymes, which modify the localized acid–base environment [31][35][36]. The C–N bond

• . The O–C–N bond between nucleobase and sugar defines the glycosidic bond. Replacement of nucleobase nitrogen by carbon results in C-nucleosides. A carbon (CH2) replacing the sugar oxygen results in carbocyclic nucleosides. When both the heteroatoms in the glycosidic bond are replaced by carbon, the

Nanoreactors for green catalysis

• M. Teresa De Martino,
• Loai K. E. A. Abdelmohsen,
• Floris P. J. T. Rutjes and
• Jan C. M. van Hest

Beilstein J. Org. Chem. 2018, 14, 716–733, doi:10.3762/bjoc.14.61

• [105]. Conversion of 4-NP in five successive cycles of reduction, catalyzed by Au@citrate, Au@PEG and Au@PEG45-b-PS65. Reprinted with permission from [121]. Copyright 2015 American Chemical Society. C–N bond formation under micellar catalyst conditions, no organic solvent involved. Adapted from

Cobalt-catalyzed directed C–H alkenylation of pivalophenone N–H imine with alkenyl phosphates

• Wengang Xu and
• Naohiko Yoshikai

Beilstein J. Org. Chem. 2018, 14, 709–715, doi:10.3762/bjoc.14.60

• -catalyzed aerobic conditions [29]. Under the same peroxide photolysis conditions (t-BuOOt-Bu with UV (254 nm) irradiation), the ortho-alkenylated imine 3aa underwent a C–N bond-forming cyclization to afford the spirocyclic imine 4 in 81% yield (Scheme 4). The reaction likely involves the initial formation

Recent advances on organic blue thermally activated delayed fluorescence (TADF) emitters for organic light-emitting diodes (OLEDs)

• Thanh-Tuân Bui,
• Fabrice Goubard,
• Malika Ibrahim-Ouali,
• Didier Gigmes and
• Frédéric Dumur

Beilstein J. Org. Chem. 2018, 14, 282–308, doi:10.3762/bjoc.14.18

5-Aminopyrazole as precursor in design and synthesis of fused pyrazoloazines

• Ranjana Aggarwal and
• Suresh Kumar

Beilstein J. Org. Chem. 2018, 14, 203–242, doi:10.3762/bjoc.14.15

• (147) with 3-oxo-3-arylpropanenitrile 15 under solvent-free grinding conditions. The reaction was proposed to proceed via formation of hydrazine by C–N bond cleavage which under reaction conditions provided 7-aminopyrazolo[1,5-a]pyrimidines 148 on coupling with 3-oxo-3-arylpropanenitrile 15 (Scheme 42

CF₃SO₂X (X = Na, Cl) as reagents for trifluoromethylation, trifluoromethylsulfenyl-, -sulfinyl- and -sulfonylation and chlorination. Part 2: Use of CF₃SO₂Cl

• Hélène Chachignon,
• Hélène Guyon and
• Dominique Cahard

Beilstein J. Org. Chem. 2017, 13, 2800–2818, doi:10.3762/bjoc.13.273

• obtained after reductive elimination of species 18. The other envisaged pathway was the oxidation of intermediate 17 through a SET to form the cationic species 19, which would then afford the final product after a C–N bond formation. Liu and co-workers also proposed a racemic version of this reaction

Vinylphosphonium and 2-aminovinylphosphonium salts – preparation and applications in organic synthesis

• Anna Kuźnik,
• Roman Mazurkiewicz and
• Beata Fryczkowska

Beilstein J. Org. Chem. 2017, 13, 2710–2738, doi:10.3762/bjoc.13.269

• subsequent 1,2-proton transfer followed by the elimination of triphenylphosphine and ring closure via formation of the new C–N bond gave the final γ-lactam derivatives 80 (Scheme 50) [66]. In 2013 Mohebat et al. used 6-amino-N,N'-dimethyluracil as an NH-acid and precursor of the carbon nucleophile in the

Recent progress in the racemic and enantioselective synthesis of monofluoroalkene-based dipeptide isosteres

• Myriam Drouin and
• Jean-François Paquin

Beilstein J. Org. Chem. 2017, 13, 2637–2658, doi:10.3762/bjoc.13.262

• C–N bond is 1.368 Å compared to 1.333 Å for the C=C bond [5][10][11][12]. Also, the amide structure is found in Nature as the s-trans or s-cis isomer, which can be in equilibrium (Figure 2b) [13]. However, most of the time it is found as the s-trans isomer to minimize steric interaction and to

One-pot three-component route for the synthesis of S-trifluoromethyl dithiocarbamates using Togni’s reagent

• Azim Ziyaei Halimehjani,
• Martin Dračínský and
• Petr Beier

Beilstein J. Org. Chem. 2017, 13, 2502–2508, doi:10.3762/bjoc.13.247

• afforded the corresponding isothiocyanate in high yield. A variable temperature NMR study revealed a rotational barrier of 14.6, 18.8, and 15.9 kcal/mol for the C–N bond in the dithiocarbamate moiety of piperidine, pyrrolidine, and diethylamine adducts, respectively. In addition, the calculated barriers of

• and trifluoromethyl groups in a single structure generates a new family of compounds with potential application as agrochemicals or in drug design. A variable temperature NMR study allowed the determination of rotational barriers of 14.6, 18.8, and 15.9 kcal/mol for the C–N bond in the dithiocarbamate

• and an increased double bond character of the C–N bond. Variable temperature 1H NMR spectra of compound 4c (CH2 region on the left and CH3 region on the right); the sample was dissolved in CDCl3. The Eyring plot obtained for the rotation around the N–C bond in compound 4c. The optimized structure of

A mechanochemical approach to access the proline–proline diketopiperazine framework

• Nicolas Pétry,
• Hafid Benakki,
• Eric Clot,
• Pascal Retailleau,
• Farhate Guenoun,
• Fatima Asserar,
• Chakib Sekkat,
• Thomas-Xavier Métro,
• Jean Martinez and
• Frédéric Lamaty

Beilstein J. Org. Chem. 2017, 13, 2169–2178, doi:10.3762/bjoc.13.217

• attack on Cb, were considered (Scheme 5). The first step was to study if there was any preferential interaction between the free nitrogen atom and either Ca or Cb before the C–N bond formation. Both optimized structures are shown in Figure 1, and compound 16a is computed to be less stable than 16b by ΔG

• = 2.7 kcal mol−1. The C···N bond distance is slightly shorter in 16b (2.673 Å) than in 16a (2.682 Å). Many attempts to locate a transition state structure for the C–N bond formation starting from either 16a or 16b failed. Even though the geometry optimizations were performed with implicit inclusion of

• the solvent influence (SMD model with methanol), the zwitterionic character developing in the C–N bond formation could not be stabilized. However, the protic methanol solvent could act both as a base to abstract the proton from the nitrogen atom, and as an acid to facilitate the C–OMe bond cleavage

Transition-metal-free synthesis of 3-sulfenylated chromones via KIO₃-catalyzed radical C(sp²)–H sulfenylation

• Yanhui Guo,
• Shanshan Zhong,
• Li Wei and
• Jie-Ping Wan

Beilstein J. Org. Chem. 2017, 13, 2017–2022, doi:10.3762/bjoc.13.199

• efforts in exploring enaminone C(sp2)–H bond sulfenylation [40][41] reactions have led us to establish the synthesis of 3-sulfenylated chromones via KIO3-catalyzed tandem reactions of o-hydroxylphenylenaminone and thiophenols via tandem C–H sulfenylation and intramolecular C–N bond oxygenation (B, Scheme

Mechanochemical synthesis of small organic molecules

• Tapas Kumar Achar,
• Anima Bose and
• Prasenjit Mal

Beilstein J. Org. Chem. 2017, 13, 1907–1931, doi:10.3762/bjoc.13.186

• acetic acid (LAG). Contrastingly, when acrylic esters were treated with 8 mol % of PdCl2 and in absence of acetic acid, β,β-diindolylpropionates were obtained as the major product (Scheme 14) [70]. C–N bond synthesis Amongst C–N bonds the amide bonds are most abundant and important too [71]. According to

• the American Chemical Society (ACS) and the Green Chemistry Institute (GCI), the “amide bond formation avoiding poor atom economy reagent” is one of the top challenges for organic chemists [72]. Easy, economical, selective and convenient approaches on C–N bond syntheses are of great importance [73][74

• nearly 90% yields for α-amino esters in 90–120 min (Scheme 18). The Ritter reaction is another significant carbon–nitrogen (C–N) bond forming reaction in the synthesis of amides [86]. Generally, a nitrile and a tertiary alcohol in presence of a strong acid react to create amides. Major drawbacks

Mechanochemical synthesis of thioureas, ureas and guanidines

• Vjekoslav Štrukil

Beilstein J. Org. Chem. 2017, 13, 1828–1849, doi:10.3762/bjoc.13.178

• –N bond of benzamide and the formation of N-acylsulfonylguanidine 48 extended by two atoms (Scheme 21b). Biguanides The attachment of an amidine subunit onto the guanidine core, which is typically accomplished by the addition of a carbodiimide molecule, leads to a biguanide framework. In a paper by

• ., DCC (78%), N-ethyl-N'-tert-butylcarbodiimide (85%) and di-p-tolylcarbodiimide (80%, Scheme 21a). The performance of the reaction was not affected even on >1 g scale. Milling 4-methyl-N-tosylbenzamide (47) with DIC and CuCl (10 mol %) for 2 hours resulted in the insertion of the carbodiimide into the C

Chiral phase-transfer catalysis in the asymmetric α-heterofunctionalization of prochiral nucleophiles

• Johannes Schörgenhumer,
• Maximilian Tiffner and
• Mario Waser

Beilstein J. Org. Chem. 2017, 13, 1753–1769, doi:10.3762/bjoc.13.170

• % yields. This obstacle could, however, be overcome by using chiral PTCs A instead, which in that cases allowed them to access the larger ring-sized products 37 in satisfying yields and with high enantioselectivities [131] (Scheme 15). α-Aminations The α-C–N bond formation of prochiral nucleophiles is one

• precursors and carry out the direct α-amination with a suitable electrophilic N-transfer reagent in the presence of a chiral catalyst to ensure an efficient face-differentiation in the C–N bond formation. This strategy has been investigated under chiral phase-transfer catalysis in the past and the results

Theoretical simulation of the infrared signature of mechanically stressed polymer solids

• Matthew S. Sammon,
• Milan Ončák and
• Martin K. Beyer

Beilstein J. Org. Chem. 2017, 13, 1710–1716, doi:10.3762/bjoc.13.165

• involving the backbone exhibit a strong force dependence [30]. What is surprising, however, is the almost complete insensitivity of the free C–O stretch. One might expect that the deformation of the amide bond in the backbone changes the electron distribution, and that the weakening of the C–N bond in the

Synthesis of alkynyl-substituted camphor derivatives and their use in the preparation of paclitaxel-related compounds

• M. Fernanda N. N. Carvalho,
• Rudolf Herrmann and
• Gabriele Wagner

Beilstein J. Org. Chem. 2017, 13, 1230–1238, doi:10.3762/bjoc.13.122

• selective with respect to the alkylation site, and the 2-alkynyl and 3-alkynyl products are formed in similar amounts. Alkynes with small substituents (e.g., heptyne or phenylacetylene) preferentially attack at the C=N bond of the sulfonylimine, suggesting that the carbon atom of the C=N is more

Regioselective (thio)carbamoylation of 2,7-di-tert-butylpyrene at the 1-position with iso(thio)cyanates

• Anna Wrona-Piotrowicz,
• Marzena Witalewska,
• Janusz Zakrzewski and
• Anna Makal

Beilstein J. Org. Chem. 2017, 13, 1032–1038, doi:10.3762/bjoc.13.102

• into 5, but to our knowledge this reaction, which must involve cleavage of the C–N bond, has no precedent in the literature (in contrast to the well-known formation of nitriles from primary thioamides, involving formal elimination of H2S [24]). Encouraged by the above results, we decided to check

Derivatives of the triaminoguanidinium ion, 5. Acylation of triaminoguanidines leading to symmetrical tris(acylamino)guanidines and mesoionic 1,2,4-triazolium-3-aminides

• Jan Szabo,
• Julian Greiner and
• Gerhard Maas

Beilstein J. Org. Chem. 2017, 13, 579–588, doi:10.3762/bjoc.13.57

• two moieties is indicated by the long C–N bond “c” (as compared to the other C–N bonds in the triazole ring) and the endocyclic N–N bond, both of which have a high single-bond character. The influence of the substituents on the triazole ring of II and 7a on the bond lengths is moderate. The bond

Pd- and Cu-catalyzed approaches in the syntheses of new cholane aminoanthraquinone pincer-like ligands

• Nikolay V. Lukashev,
• Gennadii A. Grabovyi,
• Dmitry A. Erzunov,
• Alexey V. Kazantsev,
• Gennadij V. Latyshev,
• Alexei D. Averin and
• Irina P. Beletskaya.

Beilstein J. Org. Chem. 2017, 13, 564–570, doi:10.3762/bjoc.13.55

• LiAlH4 (Scheme 2) [37]. Cu-catalyzed amination is known to be a very efficient approach for C–N bond formation [38][39]. The availability of the variety of inexpensive ligands for copper(I) is a crucial benefit in comparison to the Pd-catalyzed variant. Primary amines of different structures can readily

Thiazol-4-one derivatives from the reaction of monosubstituted thioureas with maleimides: structures and factors determining the selectivity and tautomeric equilibrium in solution

• Alena S. Pankova,
• Pavel R. Golubev,
• Alexander F. Khlebnikov,
• Alexander Yu. Ivanov and
• Mikhail A. Kuznetsov

Beilstein J. Org. Chem. 2016, 12, 2563–2569, doi:10.3762/bjoc.12.251

• tautomers exist [15][18][20][21][22][23]. (E/Z)-Isomerization of the exocyclic C=N bond of the single imino form was suggested as the cause for the dynamic effect as well [24][25]. In addition, this process complicates the interpretation of NMR spectra of thiazolidines and is a likely source of

• interconverting E/Z-isomers at the exocyclic C=N bond (given in parentheses on Scheme 2) could be involved. Therefore we have thoroughly analyzed the spectroscopic data of thiazolidine 3a from 2D NMR experiments (NOESY, 13C,1H and 15N,1H-HSQC and HMBC) and made a full assignment of all signals. A large difference

Construction of bis-, tris- and tetrahydrazones by addition of azoalkenes to amines and ammonia

• Artem N. Semakin,
• Aleksandr O. Kokuev,
• Yulia V. Nelyubina,
• Alexey Yu. Sukhorukov,
• Petr A. Zhmurov,
• Sema L. Ioffe and
• Vladimir A. Tartakovsky

Beilstein J. Org. Chem. 2016, 12, 2471–2477, doi:10.3762/bjoc.12.241

• ][6][7][8][9][10][11][12][13][14][15][16][17]. The hydrazone group is a chemically stable, easily assembled motif with prospective coordination properties, which can be tuned by substitution at the carbon and nitrogen atoms. Furthermore, a reversible E/Z-isomerism of the C=N bond allows controllable

• isomers depends on the substitution pattern and solvent. For example, the E,E-isomer was predominant for 2a in DMSO-d6, while in CDCl3 E,Z-2a was the major isomer. The assignment of stereoisomers was performed using known correlations between the configuration of the C=N bond and the chemical shift of

Robust C–C bonded porous networks with chemically designed functionalities for improved CO₂ capture from flue gas

• Damien Thirion,
• Joo S. Lee,
• Ercan Özdemir and
• Cafer T. Yavuz

Beilstein J. Org. Chem. 2016, 12, 2274–2279, doi:10.3762/bjoc.12.220

• -amidoxime the 3400 cm−1 region is even broader, due to the combination of both NH and OH stretching. The strong peak at 1664 cm−1 can be attributed to the imine C=N bond of the amidoxime structure. The textural properties were measured through nitrogen sorption isotherms at 77 K and calculated based on the