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

A metal-free approach for the synthesis of amides/esters with pyridinium salts of phenacyl bromides via oxidative C–C bond cleavage

• Kesari Lakshmi Manasa,
• Yellaiah Tangella,
• Namballa Hari Krishna and
• Mallika Alvala

Beilstein J. Org. Chem. 2019, 15, 1864–1871, doi:10.3762/bjoc.15.182

• new C–N bonds in the presence of transition metal catalysts [25][26][27][28][29][30][31][32][33][34]. Tang and Jiao reported copper catalyzed C–C single bond cleavage and C–N bond formation [35]. However, the transition metal catalysts and additives employed in these transformations are toxic and

Recent advances on the transition-metal-catalyzed synthesis of imidazopyridines: an updated coverage

• Gagandeep Kour Reen,
• Ashok Kumar and
• Pratibha Sharma

Beilstein J. Org. Chem. 2019, 15, 1612–1704, doi:10.3762/bjoc.15.165

• . The Pd-catalyzed Sonogashira reaction has successfully constructed arylated internal alkynes that are important intermediates in organic synthesis, molecular electronics and polymers [56]. C–N bond forming reactions between aryl halides and amines/amides/sulfonamides have been extensively studied in

• generation of iminyl radical intermediate 31 by homolytic cleavage of the C–N bond which was followed by reductive elimination and oxidation to yield final compound 21. Inspired by the work of Wang et al. [15] who have exploited a Cu(II)-catalyst for the construction of pyrido[1,2-a]benzimidazoles Li and Xie

• aromatic or aliphatic, only in case of triazoles substituted with an acetate group the final product was obtained in 66% yield. An open-flask, one-pot, Cu(II)-catalyzed ligand-free approach towards C–N bond formation was reported by Rasheed et al. [116]. The reaction was catalyzed by Cu(OAc)2 with cesium

Novel (2-amino-4-arylimidazolyl)propanoic acids and pyrrolo[1,2-c]imidazoles via the domino reactions of 2-amino-4-arylimidazoles with carbonyl and methylene active compounds

• Victoria V. Lipson,
• Tetiana L. Pavlovska,
• Nataliya V. Svetlichnaya,
• Anna A. Poryvai,
• Nikolay Yu. Gorobets,
• Erik V. Van der Eycken,
• Irina S. Konovalova,
• Svetlana V. Shiskina,
• Alexander V. Borisov,
• Vladimir I. Musatov and
• Alexander V. Mazepa

Beilstein J. Org. Chem. 2019, 15, 1032–1045, doi:10.3762/bjoc.15.101

• CN at 2250 cm−1. In addition, there are characteristic bands at 1664–1668 cm−1, which may include both C=C bond and the exocyclic C=N bond. Fluctuations of endocyclic C=N fragments are observed at 1584 cm−1. Thus, at least one nitrile and one NH2 group are present in the obtained compounds. The 1H

An efficient and concise access to 2-amino-4H-benzothiopyran-4-one derivatives

• Peng Li,
• Yongqi Wu,
• Tingting Zhang,
• Chen Ma,
• Ziyun Lin,
• Gang Li and
• Haihong Huang

Beilstein J. Org. Chem. 2019, 15, 703–709, doi:10.3762/bjoc.15.65

• process. The direct C–N bond formation reaction at the 2-position smoothly took place using ethylsulfinyl as the optimal leaving group and various nucleophiles such as aliphatic and aromatic amines. A variety of 2-aminobenzothiopyranones were obtained in moderate to excellent yields without the assistance

Tandem copper and photoredox catalysis in photocatalytic alkene difunctionalization reactions

• Nicholas L. Reed,
• Madeline I. Herman,
• Vladimir P. Miltchev and
• Tehshik P. Yoon

Beilstein J. Org. Chem. 2019, 15, 351–356, doi:10.3762/bjoc.15.30

• of the C–N bond-forming step, as one might expect from its proposed role in radical oxidation (Figure 1C). Conclusion These studies have demonstrated that the copper-mediated alkene difunctionalization reactions recently reported by our laboratory can be rendered catalytic in Cu(II) by adding a

DABCO- and DBU-promoted one-pot reaction of N-sulfonyl ketimines with Morita–Baylis–Hillman carbonates: a sequential approach to (2-hydroxyaryl)nicotinate derivatives

• Soumitra Guin,
• Raman Gupta,
• Debashis Majee and
• Sampak Samanta

Beilstein J. Org. Chem. 2018, 14, 2771–2778, doi:10.3762/bjoc.14.254

• -hydroxyaryl)pyridine derivatives bearing a carboxylate or a nitrile group suitably placed at C3 position of the aza-ring has been achieved in acceptable chemical yields with a broad functional group tolerance. This sequential C–C/C–N bond making process proceeds through a regioselective allylic alkylation/aza

• DABCO, followed by aromatization using DBU as a base in an open-flask has been developed. This smart oxidant metal-free C–C/C–N bond forming process leads to an array of functionalized nicotinates/nicotinonitriles possessing an interesting phenolic moiety at C6 position in good to high yields. Moreover

The mechanochemical synthesis of quinazolin-4(3H)-ones by controlling the reactivity of IBX

• Md Toufique Alam,
• Saikat Maiti and
• Prasenjit Mal

Beilstein J. Org. Chem. 2018, 14, 2396–2403, doi:10.3762/bjoc.14.216

• ]. Aryliodonium imides or iminoiodanes can be prepared by the treatment of electron-deficient amines with iodine(III). However, these compounds explode at higher temperatures [4] and hence are stored under inert atmosphere and low temperature [5]. Polyvalent iodine derivatives are versatile reagents for C–N bond

The enzymes of microbial nicotine metabolism

• Paul F. Fitzpatrick

Beilstein J. Org. Chem. 2018, 14, 2295–2307, doi:10.3762/bjoc.14.204

• the oxidation of the other C–N bond of the methyl group in N-methylaminobutyrate to form methylamine and succinate semialdehyde, an MAO reaction [39]. While the kcat/Km value of Mao with 4-aminobutyrate is only 8% that of Mabo, A. nicotinovorans grown on [14C]-nicotine produce [14C]-methylamine

• it contains covalently-bound FAD and produces hydrogen peroxide as a product in addition to 4-aminobutryate [5][38]. Mabo also catalyzes the oxidative demethylation of sarcosine. Based on these results, the mechanism of the enzyme is similar to that of sarcosine oxidase, direct oxidation of the C–N

• bond of the substrate methyl group by hydride transfer [40]. The resulting 4-aminobutryrate is likely a substrate for a chromosomally-encoded aminotransferase, producing α-ketoglutarate and succinate semialdehyde. Mao (γ-N-methylaminobutyrate oxidase) contains noncovalently-bound flavin and catalyzes

Hydroarylations by cobalt-catalyzed C–H activation

• Rajagopal Santhoshkumar and
• Chien-Hong Cheng

Beilstein J. Org. Chem. 2018, 14, 2266–2288, doi:10.3762/bjoc.14.202

• hydroarylation of glyoxylate with pyrimidine containing indoles and pyrroles 7 to provide products 63 with high productivity (Scheme 40) [79]. Similar to the imine, isocyanate is also an efficient electrophile for hydroarylation of C=N bond. It provides a high atom- and step-economical method for the preparation

Applications of organocatalysed visible-light photoredox reactions for medicinal chemistry

• Michael K. Bogdos,
• Emmanuel Pinard and
• John A. Murphy

Beilstein J. Org. Chem. 2018, 14, 2035–2064, doi:10.3762/bjoc.14.179

• molecules. An interesting report of C–N bond formation is seen in König and co-workers’ method for the formation of sulfonamidated pyrroles, using acridinium salts as photocatalysts, in the presence of oxygen and sodium hydroxide (Scheme 10) [53]. Unfortunately, this protocol was investigated for its use in

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