p-tert-Butylthiacalix[4]arenes functionalized by N-(4’-nitrophenyl)acetamide and N,N-diethylacetamide fragments: synthesis and binding of anionic guests

• Alena A. Vavilova and
• Ivan I. Stoikov

Beilstein J. Org. Chem. 2017, 13, 1940–1949, doi:10.3762/bjoc.13.188

• ][54][55][56][57]. Modified macrocycles with the amide fragments at the lower rim can form complexes with the anions by hydrogen bonds of the amide group with the guest. It was shown that (thia)calix[4]arene derivatives with urea and thiourea fragments at the lower rim can bind anions through hydrogen

A novel approach to oxoisoaporphine alkaloids via regioselective metalation of alkoxy isoquinolines

• Benedikt C. Melzer and
• Franz Bracher

Beilstein J. Org. Chem. 2017, 13, 1564–1571, doi:10.3762/bjoc.13.156

• ) at C-8 of the isoquinoline ring, which should be followed by an intramolecular trapping of the amide group to give the oxoisoaporphine bianfugecine (6, Scheme 5). However, only starting material 12 was recovered from this reaction. A D2O quenching experiment after the metalation period (4 equiv LDA

• metalation at C-6 of the benzamide moiety was not followed by an equilibration giving the desired 8’-metalated intermediate (which in turn should be trapped by the amide group to give the tetracyclic ketone 6). Probably, the DreM at C-8’ is prevented, since the amide moiety forms a chelate with a lithium ion

Bifunctional organocatalysts for the asymmetric synthesis of axially chiral benzamides

• Ryota Miyaji,
• Yuuki Wada,
• Akira Matsumoto,
• Keisuke Asano and
• Seijiro Matsubara

Beilstein J. Org. Chem. 2017, 13, 1518–1523, doi:10.3762/bjoc.13.151

• mechanism and application of this method to the construction of other axially chiral structures are currently underway and will be reported in due course. Brominating reagents. Optimization of the substituents of the amide group. Reactions were run using 1 (0.1 mmol), 3a (0.01 mmol), and 4a (0.3 mmol) in

Novel β-cyclodextrin–eosin conjugates

• Gábor Benkovics,
• Damien Afonso,
• András Darcsi,
• Szabolcs Béni,
• Sabrina Conoci,
• Éva Fenyvesi,
• Lajos Szente,
• Milo Malanga and
• Salvatore Sortino

Beilstein J. Org. Chem. 2017, 13, 543–551, doi:10.3762/bjoc.13.52

• which is assigned to the carbon atom of the amide group of the conjugates (see Figures S21 and S29 in Supporting Information File 1). In the 1H NMR spectra of both conjugates, the signals of the anomeric protons are well separated from the aromatic protons and from other CD-related resonances (Figure 4

Synthesis of spiro[isoindole-1,5’-isoxazolidin]-3(2H)-ones as potential inhibitors of the MDM2-p53 interaction

• Salvatore V. Giofrè,
• Santa Cirmi,
• Raffaella Mancuso,
• Francesco Nicolò,
• Giuseppe Lanza,
• Laura Legnani,
• Agata Campisi,
• Maria A. Chiacchio,
• Michele Navarra,
• Bartolo Gabriele and
• Roberto Romeo

Beilstein J. Org. Chem. 2016, 12, 2793–2807, doi:10.3762/bjoc.12.278

• isoxazolidine ring projects its benzyl and morpholinamide groups into the Phe19 and Leu26 pockets respectively. Likewise compounds 6b, 6d and 6g, did show a similar binding mode. Conversely, for spiro[isoxazolidin-isoindolinone] 6e, the presence of the acyclic amide group on the isoxazolidine ring produces a

Practical synthetic strategies towards lipophilic 6-iodotetrahydroquinolines and -dihydroquinolines

• David R. Chisholm,
• Garr-Layy Zhou,
• Ehmke Pohl,
• Roy Valentine and
• Andrew Whiting

Beilstein J. Org. Chem. 2016, 12, 1851–1862, doi:10.3762/bjoc.12.174

• . A further addition of 1 equivalent of DIBAL did further consume the amide (shown by a further loss of the C=O stretch by IR), however, again, progress appeared to plateau. This indicated that the reaction with the amide group was markedly faster in a non-polar solvent, and further work suggested

Reactions of N,3-diarylpropiolamides with arenes under superelectrophilic activation: synthesis of 4,4-diaryl-3,4-dihydroquinolin-2(1H)-ones and their derivatives

• Larisa Yu. Gurskaya,
• Diana S. Belyanskaya,
• Dmitry S. Ryabukhin,
• Denis I. Nilov,
• Irina A. Boyarskaya and
• Aleksander V. Vasilyev

Beilstein J. Org. Chem. 2016, 12, 950–956, doi:10.3762/bjoc.12.93

• Discussion The protonation of alkynamides 1 on both the oxygen atom of the amide group and a carbon atom of the acetylene bond in superacids or coordination of these basic centers with strong Lewis acids leads to the formation of dications A that are considered as superelectrophiles [15] (Scheme 1). These

cis–trans-Amide isomerism of the 3,4-dehydroproline residue, the ‘unpuckered’ proline

• Vladimir Kubyshkin and
• Nediljko Budisa

Beilstein J. Org. Chem. 2016, 12, 589–593, doi:10.3762/bjoc.12.57

• the crystal structures, this would indicate a destabilization of the transition state by the 3,4-double bond in Dhp and TfmDhp. Indeed, it is well known, that the peptidyl-Pro amide bond rotation proceeds via the syn/exo transition state, where the oxygen atom of the amide group moves under the

Friedel–Crafts-type reaction of pyrene with diethyl 1-(isothiocyanato)alkylphosphonates. Efficient synthesis of highly fluorescent diethyl 1-(pyrene-1-carboxamido)alkylphosphonates and 1-(pyrene-1-carboxamido)methylphosphonic acid

• Anna Wrona-Piotrowicz,
• Janusz Zakrzewski,
• Anna Gajda,
• Tadeusz Gajda,
• Anna Makal,
• Arnaud Brosseau and
• Rémi Métivier

Beilstein J. Org. Chem. 2015, 11, 2451–2458, doi:10.3762/bjoc.11.266

• structure is shown in Figure 6. The pyrenyl moiety in 3a is slightly bent, the angle between the planes of rings C1–C2–C15–C14–C13–C12 and C5–C6–C7–C8–C9–C16 is 4.23(13)°. The amide group is twisted by 57.1(2) degrees from the plane of the C1–C2–C15–C14–C13–C12 ring. Together with the C1–C17 bond length

• exceeding 1.5 Å, this suggests that there is only very weak electronic conjugation between these units. The phosphonato group is also almost perpendicular to the plane of the amide group; the relevant C17–N1–C18–P1 torsion angle is 102.39(13)°. The most important geometrical parameters and intermolecular

Conformational equilibrium in supramolecular chemistry: Dibutyltriuret case

• Karina Mroczyńska,
• Małgorzata Kaczorowska,
• Erkki Kolehmainen,
• Ireneusz Grubecki,
• Marek Pietrzak and
• Borys Ośmiałowski

Beilstein J. Org. Chem. 2015, 11, 2105–2116, doi:10.3762/bjoc.11.227

• interactions [41] that act diagonally between neighbouring hydrogen bonding sites. The breakage of single intramolecular hydrogen bonding upon association leading to rotamerism was our motivation to search for more complex systems than previously reported [2][9][10]. Since the amide group is common in

First principle investigation of the linker length effects on the thermodynamics of divalent pseudorotaxanes

• Andreas J. Achazi,
• Doreen Mollenhauer and
• Beate Paulus

Beilstein J. Org. Chem. 2015, 11, 687–692, doi:10.3762/bjoc.11.78

• temperature or solvent effects. Including the counter ion in the determination of ΔG has a much weaker effect in the divalent case compared to the monovalent one, because the guest molecule is larger and the positive charge of the amide group can be distributed better over the molecule. For the divalent

Highly selective electrochemical fluorination of dithioacetal derivatives bearing electron-withdrawing substituents at the position α to the sulfur atom using poly(HF) salts

• Bin Yin,
• Shinsuke Inagi and
• Toshio Fuchigami

Beilstein J. Org. Chem. 2015, 11, 85–91, doi:10.3762/bjoc.11.12

• . In sharp contrast, in the latter two cases, fluorination product selectivity was strongly affected by the electron-withdrawing ability of α-substituents: A dithioacetal bearing a relatively weak electron-withdrawing amide group provided a fluorodesulfurization product selectively while a dithioacetal

• substrates. It is known that the acidity of the α-proton of N,N-diethylacetoamide is 4 to 5 times lower than that of acetone and ethyl acetate [35]. Therefore, the acidity of the α-proton of 1f having an amide group would be much lower compared to that of 1b and 1d having an ester and acetyl group

• the acidity of α-protons of acetoamides is much lower compared to that of acetate and acetone as mentioned. Therefore, it is understandable that the anodic fluorination of 1f having a weakly electron-withdrawing amide group resulted in fluorodesulfurization to provide 3f even when Et3N·3HF containing

The unexpected influence of aryl substituents in N-aryl-3-oxobutanamides on the behavior of their multicomponent reactions with 5-amino-3-methylisoxazole and salicylaldehyde

• Volodymyr V. Tkachenko,
• Elena A. Muravyova,
• Sergey M. Desenko,
• Oleg V. Shishkin,
• Svetlana V. Shishkina,
• Dmytro O. Sysoiev,
• Thomas J. J. Müller and
• Valentin A. Chebanov

Beilstein J. Org. Chem. 2014, 10, 3019–3030, doi:10.3762/bjoc.10.320

• was described for analogous three-component reactions [27][28]. The structures of all synthesized compounds were unambiguously established by elemental analysis, MS, NMR spectroscopy and X-ray analysis. Thus, the 1H NMR spectrum of chroman-3-carboxamide 4a exhibits a singlet for the NH amide group at

Recent advances in the electrochemical construction of heterocycles

• Robert Francke

Beilstein J. Org. Chem. 2014, 10, 2858–2873, doi:10.3762/bjoc.10.303

• deprotonation of the amide group. According to the authors, the deprotonation is followed by ring closure on the C–C-triple bond, generating a carbanion intermediate which is then protonated by the solvent. For sufficient cyclization rates, the reaction mixture has to be heated to 80 °C. Various alkynylanilines

Improving the reactivity of phenylacetylene macrocycles toward topochemical polymerization by side chains modification

• Simon Rondeau-Gagné,
• Jules Roméo Néabo,
• Maxime Daigle,
• Katy Cantin and
• Jean-François Morin

Beilstein J. Org. Chem. 2014, 10, 1613–1619, doi:10.3762/bjoc.10.167

• supramolecular nanotubular structures [33][34][35][36][37][38]. Among other things, we have shown that inversion of the amide group configuration (acetanilide vs benzamide) at two different positions on phenylacetylene macrocycles (PAMs) leads to significant changes of the gelation properties and, consequently

Consecutive isocyanide-based multicomponent reactions: synthesis of cyclic pentadepsipeptoids

• Angélica de Fátima S. Barreto,
• Otilie E. Vercillo,
• Ludger A. Wessjohann and
• Carlos Kleber Z. Andrade

Beilstein J. Org. Chem. 2014, 10, 1017–1022, doi:10.3762/bjoc.10.101

• in combinatorial synthesis [40][41][42][43] and can be used strategically for the synthesis of depsipeptoids. By analogy to peptides and peptoids, a depsipeptoid would be a peptoid bearing an ester group instead of an amide group. Differences between peptide, peptoid, depsipeptide and depsipeptoid

Tuning the interactions between electron spins in fullerene-based triad systems

• Maria A. Lebedeva,
• Thomas W. Chamberlain,
• E. Stephen Davies,
• Bradley E. Thomas,
• Martin Schröder and
• Andrei N. Khlobystov

Beilstein J. Org. Chem. 2014, 10, 332–343, doi:10.3762/bjoc.10.31

• m/z 791 and the solid state IR spectrum as a pressed disc in KBr indicated only one signal in the carbonyl region characteristic of the amide group (1653 cm−1) and no signal related to the carboxylic group stretch. The desired carboxylic acid compound [12] seems to be unstable under acidic

• electron withdrawing amide group from the α-position of the carboxylate functionality, while maintaining an identical inter-fullerene separation in the asymmetric triad when compared with the symmetric analogue (Scheme 3). The key step in this procedure is the formation of intermediate compound 14 via the

Efficient carbon-Ferrier rearrangement on glycals mediated by ceric ammonium nitrate: Application to the synthesis of 2-deoxy-2-amino-C-glycoside

• Alafia A. Ansari,
• Y. Suman Reddy and
• Yashwant D. Vankar

Beilstein J. Org. Chem. 2014, 10, 300–306, doi:10.3762/bjoc.10.27

• rearrangement took place from the axial side, as expected, since the hydroxy group at C-4 is axially oriented in compound 9. Moreover, the dihydroxylation took place from the side opposite to the amino group at C-2, which can be attributed to the steric hindrance from the bulky amide group. A D-galacto

Structure of 1,5-benzodiazepinones in the solid state and in solution: Effect of the fluorination in the six-membered ring

• Marta Pérez-Torralba,
• Rosa M. Claramunt,
• M. Ángeles García,
• Concepción López,
• M. Carmen Torralba,
• M. Rosario Torres,
• Ibon Alkorta and
• José Elguero

Beilstein J. Org. Chem. 2013, 9, 2156–2167, doi:10.3762/bjoc.9.253

• P21/c space group containing one molecule per asymmetric unit (Figure 3; the numbering used in the crystallographic part is different from that of Figure 1). The bonding distances and angles agree with the electronic distribution according to one amide group on the C1 atom and one double bond, C3–N2

• , respectively. These molecules are linked forming dimers by symmetric hydrogen bonds between the amide group and the carbonyl oxygen atom of an adjacent one (distances N1H1···O1’ 1.932(2) Å and N1···O1’ 2.877(2) Å; angle NHO 162.7(1)º). These dimers interact by double intermolecular F–F contacts between the F5

Synthesis of the reported structure of piperazirum using a nitro-Mannich reaction as the key stereochemical determining step

• James C. Anderson,
• Andreas S. Kalogirou,
• Michael J. Porter and
• Graham J. Tizzard

Beilstein J. Org. Chem. 2013, 9, 1737–1744, doi:10.3762/bjoc.9.200

• of resonance which would result in the formation of the E iPr group and the planar amide group during formation of 23. Reduction of the double bond with hydrogen over palladium on charcoal gave a single diastereoisomer 25 in quantitative yield. In one dimensional nOe studies irradiation of H-3 (δ

Molecular assembly of amino acid interlinked, topologically symmetric, π-complementary donor–acceptor–donor triads

• M. B. Avinash,
• K. V. Sandeepa and
• T. Govindaraju

Beilstein J. Org. Chem. 2013, 9, 1565–1571, doi:10.3762/bjoc.9.178

• interactions with the proton of the α-carbon and the side chain functionality of the interlinking amino acid, which suggests a trans configuration for the amide group. Powder X-ray diffraction (PXRD) studies for aggregates of 1, 2 and 3 showed a broad peak corresponding to d-spacing of ~3.4 Å, indicating a

Study on the total synthesis of velbanamine: Chemoselective dioxygenation of alkenes with PIFA via a stop-and-flow strategy

• Huili Liu,
• Kuan Zheng,
• Xiang Lu,
• Xiaoxia Wang and
• Ran Hong

Beilstein J. Org. Chem. 2013, 9, 983–990, doi:10.3762/bjoc.9.113

• cyclization to form an iminolactone (such as the intermediate C in Scheme 6). Thus, if the original amide group could be recovered, it may “flow” into the second round of alkene dioxygenation. This “stop-and-flow” approach easily differentiates two alkene groups during the synthetic endeavor. In our

Enantioselective reduction of ketoimines promoted by easily available (S)-proline derivatives

• Martina Bonsignore,
• Maurizio Benaglia,
• Laura Raimondi,
• Manuel Orlandi and
• Giuseppe Celentano

Beilstein J. Org. Chem. 2013, 9, 633–640, doi:10.3762/bjoc.9.71

• involves the formation of a hydrogen-bond between the amide group of the catalyst and the substrate as a necessary element for stereocontrol (for another example of relevant N-formyl proline derivative see [12]). Also in Sun catalysts F [13][14] and sulfinamide G [15] as well as in chiral picolinamides H

• , reported by Zhang [16][17] and intensely studied by our group [18][19][20][21][22][23], the presence of the acidic hydrogen of the amide group is essential for the stereochemical efficiency of the metal-free catalyst. Based on these considerations we decided to investigate the use of a strong hydrogen-bond

Inter- and intramolecular enantioselective carbolithiation reactions

• Asier Gómez-SanJuan,
• Nuria Sotomayor and
• Esther Lete

Beilstein J. Org. Chem. 2013, 9, 313–322, doi:10.3762/bjoc.9.36

• amide group favors a fast cyclization at low temperature, and pyrroloisoquinoline 50b is isolated in good yield. However, this higher reactivity results in a low enantioselection when (−)-sparteine (L1) is used as chiral ligand, under various reaction conditions [34]. Similarly, the intramolecular

• carbolithiation of N-alkenyl substituted o-iodoanilines 51 affords enantiomerically enriched 2,4-disubstituted tetrahydroquinolines 52 and 53 by using (−)-sparteine (L1) as chiral ligand [52]. An amide group is also required to favor the cyclization, and also has an important effect in both the

Metal-mediated aminocatalysis provides mild conditions: Enantioselective Michael addition mediated by primary amino catalysts and alkali-metal ions

• Matthias Leven,
• Jörg M. Neudörfl and
• Bernd Goldfuss

Beilstein J. Org. Chem. 2013, 9, 155–165, doi:10.3762/bjoc.9.18

• -sulfobenzoic moiety according to TS-14a–d (Figure 3 and Figure 4). This conformation allows the formation of an intramolecular bond between the lithium ion and the nitrogen of the amide group. A similar structural property is found in the X-ray crystallographic structure of compound 5 (Figure 1). The same