Deoxygenative C2-heteroarylation of quinoline N-oxides: facile access to α-triazolylquinolines

• Geetanjali S. Sontakke,
• Rahul K. Shukla and
• Chandra M. R. Volla

Beilstein J. Org. Chem. 2021, 17, 485–493, doi:10.3762/bjoc.17.42

• significant interest in the last few years [12][13]. In particular, the C2-functionalization of quinolines has been well studied, and various methodologies were established for C–C [14][15][16][17][18][19][20][21][22][23], C–O [24][25] and C–S [26][27] bond formation. Recently C2-selective C–N bond formation

• purified by column chromatography (ethyl acetate/petroleum ether 1:9) to get the desired product 3a in 92% yield (50 mg, 0.18 mmol). Bioactive molecules containing the 2-aminoquinoline motif. C2-selective C–N bond formation of N-oxides. Substrate scope of N-sulfonyl-1,2,3-triazoles. Reaction conditions: 1a

1,2,3-Triazoles as leaving groups: S_NAr reactions of 2,6-bistriazolylpurines with O- and C-nucleophiles

• Dace Cīrule,
• Irina Novosjolova,
• Ērika Bizdēna and
• Māris Turks

Beilstein J. Org. Chem. 2021, 17, 410–419, doi:10.3762/bjoc.17.37

• 4a. Also hydrolysis of 2c into 4b proceeded under mild conditions and only gentle warming to 50 °C was required. 2,6-Bistriazolylpurine derivatives in SNAr reactions with C-nucleophiles Next, SNAr reactions between 2,6-bistriazolylpurine 2c and C-nucleophiles offered an easy way for the C–N bond

Mesoionic tetrazolium-5-aminides: Synthesis, molecular and crystal structures, UV–vis spectra, and DFT calculations

• Vladislav A. Budevich,
• Sergei V. Voitekhovich,
• Alexander V. Zuraev,
• Vadim E. Matulis,
• Vitaly E. Matulis,
• Alexander S. Lyakhov,
• Ludmila S. Ivashkevich and
• Oleg A. Ivashkevich

Beilstein J. Org. Chem. 2021, 17, 385–395, doi:10.3762/bjoc.17.34

• cation, shown in Figure 2, and two bromide anions. The structure of the cation is close to C2 symmetry, with an rms deviation of its non-hydrogen atoms from ideal positions of 0.1320 Å. In the salt 9, the lengths of the tetrazole ring bonds and the exocyclic C–N bond are given in Table 3 together with

CF₃-substituted carbocations: underexploited intermediates with great potential in modern synthetic chemistry

• Anthony J. Fernandes,
• Armen Panossian,
• Bastien Michelet,
• Agnès Martin-Mingot,
• Frédéric R. Leroux and
• Sébastien Thibaudeau

Beilstein J. Org. Chem. 2021, 17, 343–378, doi:10.3762/bjoc.17.32

1,2,3-Triazoles as leaving groups in S_NAr–Arbuzov reactions: synthesis of C6-phosphonated purine derivatives

• Kārlis-Ēriks Kriķis,
• Irina Novosjolova,
• Anatoly Mishnev and
• Māris Turks

Beilstein J. Org. Chem. 2021, 17, 193–202, doi:10.3762/bjoc.17.19

• new method for C–N bond transformations into C–P bonds was developed using 1,2,3-triazoles as leaving groups in SNAr–Arbuzov reactions. A series of C6-phosphonated 2-triazolylpurine derivatives was synthesized for the first time, with the isolated yields reaching up to 82% in the C–P-bond-forming

Recent progress in the synthesis of homotropane alkaloids adaline, euphococcinine and N-methyleuphococcinine

• Dimas J. P. Lima,
• Antonio E. G. Santana,
• Michael A. Birkett and
• Ricardo S. Porto

Beilstein J. Org. Chem. 2021, 17, 28–41, doi:10.3762/bjoc.17.4

• . After the treatment of (−)-46 with the lithium acetylide ethylenediamine complex in THF, a nucleophilic alkynylation occurred, with a reversal of configuration in the reaction center. Then, removal of the 1-(2-hydroxyphenyl)ethyl group via cleavage of the C–N bond, leading to (6S)-ethynylpiperidine

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

• likely starts from the addition of the fluorinated radical to the C=N bond followed by a conversion of the nitroxyl radical via hydrogen atom transfer [26][27] providing hydroxylamine 4. At the next stage, the intramolecular N-alkylation occurs leading to an N-oxide. This step of nucleophilic

Ultrasound-assisted Strecker synthesis of novel 2-(hetero)aryl-2-(arylamino)acetonitrile derivatives

• Emese Gal,
• Luiza Gaina,
• Hermina Petkes,
• Alexandra Pop,
• Castelia Cristea,
• Gabriel Barta,
• Dan Cristian Vodnar and
• Luminiţa Silaghi-Dumitrescu

Beilstein J. Org. Chem. 2020, 16, 2929–2936, doi:10.3762/bjoc.16.242

• nucleophile to an imine C–N bond. Among the various cyanide transferring agents, which were largely documented in the search for advantageous synthetic procedures of these synthetic intermediates [17], trimethylsilyl cyanide (TMSCN) gave the possibility of accomplishing Strecker reactions using a wide variety

• recorded suggesting the reduced mobility for the proton in the amino group. The presence of the cyano functional group was confirmed by the FTIR spectra displaying an absorption band typical for the stretching vibration of the C≡N bond situated in the 2230–2260 cm−1 region, its position appearing slightly

Synthesis of purines and adenines containing the hexafluoroisopropyl group

• Viacheslav Petrov,
• Rebecca J. Dooley,
• Alexander A. Marchione,
• Elizabeth L. Diaz,
• Brittany S. Clem and
• William Marshall

Beilstein J. Org. Chem. 2020, 16, 2739–2748, doi:10.3762/bjoc.16.224

• 3b was a sharp and well-resolved doublet (δ = −69.95 ppm, JFH = 6.9 Hz in CDCl3), the analogous resonance in the major isomer 3a was significantly broadened (δ = −68.95 ppm, ∆√1/2 = 60Hz, CDCl3), indicating a restricted rotation around the C–N bond, likely due to the steric interaction of the CF3

• mentioned above, the broadening of the resonances corresponding to the CF3 group as observed in the 19F NMR spectra of derivatives 3a, 4a, and 4b at ambient temperature is likely to be related to a restricted rotation around the C–N bond as a result of the steric interaction between the fluorine atoms of

Selective and reversible 1,3-dipolar cycloaddition of 6-aryl-1,5-diazabicyclo[3.1.0]hexanes with 1,3-diphenylprop-2-en-1-ones under microwave irradiation

• Alexander P. Molchanov,
• Mariia M. Efremova,
• Mariya A. Kryukova and
• Mikhail A. Kuznetsov

Beilstein J. Org. Chem. 2020, 16, 2679–2686, doi:10.3762/bjoc.16.218

• AMIs can be generated in situ by thermal opening of any C–N bond of the diaziridine ring in 6-aryl-substituted 1,5-diazabicyclo[3.1.0]hexanes or 7-aryl-substituted 1,6-diazabicyclo[4.1.0]heptanes, respectively [16][17]. For the thermal generation conditions, the 1,3-dipolar cycloadditions of AMIs were

• on the catalytic cleavage of the C–N bond in the diaziridine ring under the influence of Lewis acids [23][24]. However, the selectivity of the cycloaddition for thermal or catalytic conditions can be different [25]. It was possible to obtain the cycloaddition products of unstable azomethine imines

Chan–Evans–Lam N1-(het)arylation and N1-alkеnylation of 4-fluoroalkylpyrimidin-2(1H)-ones

• Viktor M. Tkachuk,
• Oleh O. Lukianov,
• Mykhailo V. Vovk,
• Isabelle Gillaizeau and
• Volodymyr A. Sukach

Beilstein J. Org. Chem. 2020, 16, 2304–2313, doi:10.3762/bjoc.16.191

• corresponding pyrimidines. An efficient C–N bond-forming process is also observed by using boronic acid pinacol esters as coupling partners in the presence of Cu(II) acetate and boric acid. The 4-fluoroalkyl group on the pyrimidine ring significantly assists in the formation of the target N1-substituted

Synthetic approaches to bowl-shaped π-conjugated sumanene and its congeners

• Shakeel Alvi and
• Rashid Ali

Beilstein J. Org. Chem. 2020, 16, 2212–2259, doi:10.3762/bjoc.16.186

• bowl structure as compared to the pristine buckybowls containing all-carbon atoms in their frameworks. In sharp contrast, deeper bowl structure (1.30 Å) was observed in the case of triazasumanene as compared to the pristine sumanene (1.11Å) since the C–N bond length (1.47 Å) is shorter compared to the

Access to highly substituted oxazoles by the reaction of α-azidochalcone with potassium thiocyanate

• Mysore Bhyrappa Harisha,
• Pandi Dhanalakshmi,
• Rajendran Suresh,
• Raju Ranjith Kumar and
• Shanmugam Muthusubramanian

Beilstein J. Org. Chem. 2020, 16, 2108–2118, doi:10.3762/bjoc.16.178

• , the following plausible mechanism for the formation of 2,4,5-trisubstituted oxazoles can be proposed (Scheme 7). It is known that the thiocyanate radical is generated from potassium thiocyanate by the reaction with potassium persulfate [72]. The N-end of thiocyanate radical reacts with the C=N bond to

Syntheses of spliceostatins and thailanstatins: a review

• William A. Donaldson

Beilstein J. Org. Chem. 2020, 16, 1991–2006, doi:10.3762/bjoc.16.166

• endpoint. However, Nicolaou’s route is the shortest (6 or 7 steps, 9.8–9.2% yield), while Kitahara’s synthesis is the highest-yielding and does not involve the use of expensive transition metals or organocatalysts. Syntheses to generate the C-14 stereocenter via C–N bond formation Two groups implemented

• strategies that rely on the generation of the C-14 stereocenter by stereoselective C–N bond formation. The Jacobsen group utilized an asymmetric Cr(III)-catalyzed cycloaddition reaction [27] between (2Z,4E)-3-(triethylsilyloxy)-2,4-hexadiene (40) and the aldehyde 41 to generate the 4-silyloxydihydropyran 43

A complementary approach to conjugated N-acyliminium formation through photoredox-catalyzed intermolecular radical addition to allenamides and allencarbamates

• Olusesan K. Koleoso,
• Matthew Turner,
• Felix Plasser and
• Marc C. Kimber

Beilstein J. Org. Chem. 2020, 16, 1983–1990, doi:10.3762/bjoc.16.165

• nucleophilic addition at the α-position giving the observed N,N’-allylaminal product 43. Conversely, addition of a nucleophile at the γ-position of E-42 gives the observed Z-enamide 44; and addition at the γ-position of Z-42’ gives the same observed Z-enamide 44 after C–N bond rotation. Conclusion In

One-pot synthesis of oxazolidinones and five-membered cyclic carbonates from epoxides and chlorosulfonyl isocyanate: theoretical evidence for an asynchronous concerted pathway

• Esra Demir,
• Ozlem Sari,
• Yasin Çetinkaya,
• Ufuk Atmaca,
• Safiye Sağ Erdem and
• Murat Çelik

Beilstein J. Org. Chem. 2020, 16, 1805–1819, doi:10.3762/bjoc.16.148

• ′ (Figure 2). Therefore, attack by N4 of CSI on the C2 of epoxide is found to be energetically the most favored approach. The epoxide ring opening and formation of the O–C(=O) bond are almost completed before the C–N bond is formed. The changes in bond lengths along the intrinsic reaction coordinate (IRC

Photocatalyzed syntheses of phenanthrenes and their aza-analogues. A review

• Alessandra Del Tito,
• Havall Othman Abdulla,
• Davide Ravelli,
• Stefano Protti and
• Maurizio Fagnoni

Beilstein J. Org. Chem. 2020, 16, 1476–1488, doi:10.3762/bjoc.16.123

• formed by an intramolecular C–C or C–N bond-formation event, as detailed in the following. 2.1 Synthesis of phenanthridines via photocatalyzed intramolecular C–C bond formation A typical approach makes use of imidoyl radicals [30][44] as the key intermediates. Among the different methods proposed to

• proximity to each other, prone to be engaged in a bidentate-type metal-coordination complex [75]. 2.2 Synthesis of phenanthridines via photocatalyzed C–N bond formation As mentioned in the introduction, the examples gathered here involve the intermediacy of N-centered radicals. As a representative case, the

Oxime radicals: generation, properties and application in organic synthesis

• Igor B. Krylov,
• Stanislav A. Paveliev,
• Alexander S. Budnikov and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2020, 16, 1234–1276, doi:10.3762/bjoc.16.107

• rule, a C–O bond is formed in intermolecular reactions, intramolecular cyclization generally occurs with the formation of a five-membered cycle of isoxazoline (C–O bond formation) or nitrone (C–N bond formation). Application of the oxime radicals in organic synthesis: intermolecular reactions Selective

• or 61). As a result of the reaction, a 5-membered cycle is formed via the formation of C–O (products 58 and 60) or C–N bond (product 61) in accordance with the ability of oxime radicals to act as O- or N-radicals. The formation of the heterocycles, mainly isoxazolines/isoxazoles, from unsaturated

Copper catalysis with redox-active ligands

• Agnideep Das,
• Yufeng Ren,
• Cheriehan Hessin and
• Marine Desage-El Murr

Beilstein J. Org. Chem. 2020, 16, 858–870, doi:10.3762/bjoc.16.77

• selectivity. Homo- and cross-coupling adducts 16a and 16b–g were obtained from the corresponding phenols (14a–e and 15a–c) as shown in the bottom of Scheme 9 with high chemoselectivity. C–N bond formation While copper complexes are at the heart of oxidative biological networks, the introduction of nitrogen is

• a different matter. The Arnold group has elegantly shown that through iterative mutagenesis “directed evolution” enzymes can be coaxed to perform unnatural transformations such as C–N bond forming aziridination, which has no biological counterpart [33]. While the exact structure of the mutant

• metalloenzymatic active site was not characterized in detail, it might bear some resemblance to the original biological active site. Building on their previously discussed phenol oxidation methodology (Scheme 5 and Scheme 6), Lumb and co-workers have targeted subsequent C–N bond formation to access oxindoles [34

A systematic review on silica-, carbon-, and magnetic materials-supported copper species as efficient heterogeneous nanocatalysts in “click” reactions

• Pezhman Shiri and
• Jasem Aboonajmi

Beilstein J. Org. Chem. 2020, 16, 551–586, doi:10.3762/bjoc.16.52

• catalysts; Sharpless–Meldal C–N bond-forming reaction; silica/carbon/magnetic materials; Introduction Heterocycles are a class of organic compounds with significant biological activities [1][2][3][4][5][6][7][8][9][10], including antimicrobial [2], antibacterial [3], anti-HIV [4], antiviral [5

• = Cu/Au molar ratio, Gx = dendrimer generation, and AAA = dendron type). After the preparation and characterization of the CuYAu–Gx-AAA–SBA-15 catalyst, the material was employed in a triazole synthesis, and it was established that the catalyst was efficient in the Sharpless–Meldal C–N bond formation

KOt-Bu-promoted selective ring-opening N-alkylation of 2-oxazolines to access 2-aminoethyl acetates and N-substituted thiazolidinones

• Qiao Lin,
• Shiling Zhang and
• Bin Li

Beilstein J. Org. Chem. 2020, 16, 492–501, doi:10.3762/bjoc.16.44

• to synthesize thiazolidinone derivatives through a Barton–McCombie pathway in 2015 [17] (Scheme 1b). Recently, potassium tert-butoxide has been shown to be an efficient promoter for C–C-bond formation reactions [18][19][20][21][22]. However, only few reports described C–N-bond cross-coupling

• directly obtained without reaction of C≡N bond. Substrates with pyridyl and thiophene groups were also applied to the synthesis of the corresponding thiazolidine derivatives 5j and 5k in 77% and 50% yields, respectively. On the other hand, further transformation of the 2-aminoethyl acetate product 3a was

• promote this type of reaction, but also acts as a nucleophilic oxygen donor during the C=N bond cleavage process to lead the corresponding 2-aminoethyl acetates. To gain insight into the reaction mechanism, the reaction was repeated in the presence of radical scavengers to evaluate if a radical process is

Architecture and synthesis of P,N-heterocyclic phosphine ligands

• Wisdom A. Munzeiwa,
• Bernard Omondi and
• Vincent O. Nyamori

Beilstein J. Org. Chem. 2020, 16, 362–383, doi:10.3762/bjoc.16.35

• chlorodiphenylphosphine, afforded 1-methyl-4,5-bis(diphenylphosphino)imidazole (85). Finally, N-methylation gave the imidazolium salt derivative 86 in good yield (65%). Preparation of N-heterocyclic phosphines via metal-catalyzed P–C/N bond formation There is limited availability of certain N-containing precursors and

Palladium-catalyzed Sonogashira coupling reactions in γ-valerolactone-based ionic liquids

• László Orha,
• József M. Tukacs,
• László Kollár and
• László T. Mika

Beilstein J. Org. Chem. 2019, 15, 2907–2913, doi:10.3762/bjoc.15.284

• iodide (Table 3, entries 2–7). Under identical conditions, 2-iodothiophene, and iodopyridine derivatives could also easily be converted to the corresponding acetylene with good or even excellent isolated yields (3i–n). When 2-amino-3-iodopyridine (1i) was converted no C–N bond formation was detected

Photoreversible stretching of a BAPTA chelator marshalling Ca²⁺-binding in aqueous media

• Aurélien Ducrot,
• Arnaud Tron,
• Robin Bofinger,
• Ingrid Sanz Beguer,
• Jean-Luc Pozzo and
• Nathan D. McClenaghan

Beilstein J. Org. Chem. 2019, 15, 2801–2811, doi:10.3762/bjoc.15.273

• photochemically active groups has been used to trigger the decrease of the ligand’s affinity for calcium ions leading to photorelease [12][13][14], and as such has proved an alternative to C–N-bond photocleavage [15][16]. A molecular prototype for the photodecaging of calcium was Nitr-5, where an electron

Excited state dynamics for visible-light sensitization of a photochromic benzil-subsituted phenoxyl-imidazolyl radical complex

• Yoichi Kobayashi,
• Yukie Mamiya,
• Katsuya Mutoh,
• Hikaru Sotome,
• Masafumi Koga,
• Hiroshi Miyasaka and
• Jiro Abe

Beilstein J. Org. Chem. 2019, 15, 2369–2379, doi:10.3762/bjoc.15.229

• similar to that of PIC and because the fast decay component does not depend on the molecular oxygen, the fast and slow decay components can be assigned to the biradical form generated by the C–N bond breaking and the T1 state of Benzil-PIC, respectively. It is worth mentioning that the T1 state of Benzil

• biradical generated instantaneously, respectively. It indicates that the biradical was also formed by the direct excitation of the PIC unit with 400 nm light. The spectral evolution from EAS1 (160 fs, grey line in Figure 3d) to EAS2 (1.4 ps, red line in Figure 3d) shows the C–N bond cleavage of the PIC unit

• and the spectral shift due to the benzil unit (from 582 nm to 556 nm). In PABI, which is a similar photochromic molecule to PIC, it was reported that the C–N bond fission occurs with the time constant of 140 fs and the broad absorption assigned to the biradical form was formed with a time constant of