Iron complexes of tetramine ligands catalyse allylic hydroxyamination via a nitroso–ene mechanism

• David Porter,
• Belinda M.-L. Poon and
• Peter J. Rutledge

Beilstein J. Org. Chem. 2015, 11, 2549–2556, doi:10.3762/bjoc.11.275

• partner, BocNH2 (12) was isolated in increased yield (25%). This mirrors the results of Jørgensen and Nicholas who have observed an analogous iron-catalysed reduction of N-phenylhydroxylamine to aniline, and confirms that FeTPA (4) can mediate the conversion of BocNHOH to BocNH2. Nitroso species can be

Efficient synthetic protocols for the preparation of common N-heterocyclic carbene precursors

• Morgan Hans,
• Jan Lorkowski,
• Albert Demonceau and
• Lionel Delaude

Beilstein J. Org. Chem. 2015, 11, 2318–2325, doi:10.3762/bjoc.11.252

• NHC, two equivalents of a primary alkylamine or aniline, to introduce the N1 and N3 modular units, and a suitable C1 building block for joining the precarbenic C2 center (Scheme 2). An additional reduction of the intermediate diimines into diamines is required prior to the assembly of the

• and ZnCl2. This Friedel–Crafts alkylation was carried out under solvent-free conditions and afforded high yields of the bulky aniline needed to follow the Arduengo formylative cyclization path. It was originally performed in a sealed tube under autogeneous pressure at 160 °C. We checked that the

Recent advances in copper-catalyzed C–H bond amidation

• Jie-Ping Wan and
• Yanfeng Jing

Beilstein J. Org. Chem. 2015, 11, 2209–2222, doi:10.3762/bjoc.11.240

• sulfonamidation of 2-arylpyridines via C–H activation. Besides the peroxide-free advantage, the C–H amination using aniline was found applicable to allow the synthesis of biarylamine. More recently, based on the DG strategy, the Yu group [59] designed the o-amidation of arylamides with copper catalysis under

Profluorescent substrates for the screening of olefin metathesis catalysts

• Raphael Reuter and
• Thomas R. Ward

Beilstein J. Org. Chem. 2015, 11, 1886–1892, doi:10.3762/bjoc.11.203

• -methoxynaphthalene-1-sulfonamide moiety that is connected by an internal double bond to a 2,4-dinitroaniline core, acting as a fluorescence quencher [17]. Both the sulfonamide of the fluorophore and the aniline group of the quencher bear another allyl group. Upon relay ring-closing metathesis, the fluorophore and

• product. A strong base (e.g., NaH) was crucial to achieve complete deprotonation of the highly deactivated aniline [26]. The fluorophore and quencher parts were finally connected in high yield relying on a nucleophilic substitution. Ring-closing metathesis of substrates With the aim of miniaturizing and

Cross metathesis of unsaturated epoxides for the synthesis of polyfunctional building blocks

• Meriem K. Abderrezak,
• Kristýna Šichová,
• Nancy Dominguez-Boblett,
• Antoine Dupé,
• Zahia Kabouche,
• Christian Bruneau and
• Cédric Fischmeister

Beilstein J. Org. Chem. 2015, 11, 1876–1880, doi:10.3762/bjoc.11.201

• post-transformation of 4 by ring-opening of the epoxide moiety. The diol 6, methoxy alcohol 7 and amino alcohol 8 were thus prepared by reacting 4 with water, sodium methoxide and aniline, respectively (Scheme 4). The synthesis of 6 proceeded cleanly and did not require any purification procedure (see

An efficient synthesis of N-substituted 3-nitrothiophen-2-amines

• Sundaravel Vivek Kumar,
• Shanmugam Muthusubramanian,
• J. Carlos Menéndez and
• Subbu Perumal

Beilstein J. Org. Chem. 2015, 11, 1707–1712, doi:10.3762/bjoc.11.185

• -(1-(methylthio)-2-nitrovinyl)aniline (1e, 1 mmol) and 1,4-dithiane-2,5-diol (2, 0.5 mmol, 1 equiv) was performed. Initially, this model reaction was attempted in ethanol and in the absence of base, with negative results (Table 1, entry 1). In the presence of TEA (1 equiv), it gave 62% yield (Table 1

Pyridinoacridine alkaloids of marine origin: NMR and MS spectral data, synthesis, biosynthesis and biological activity

• Louis P. Sandjo,
• Victor Kuete and
• Maique W. Biavatti

Beilstein J. Org. Chem. 2015, 11, 1667–1699, doi:10.3762/bjoc.11.183

• steps with a 25% overall yield. The reaction started with methyl 2,5-dimethoxy-3-nitrobenzoate, which was reduced into the corresponding aniline under hydrogen conditions with palladium on carbon. The aniline was further treated with Meldrum’s acid and trimethyl orthoformate to afford an enamine which

• to N-(tert-butoxycarbonyl)-2-(trimethylstannyl)aniline using Stille conditions. The expected compound was obtained along with the N-Boc-protected subarine. The treatment of both compounds with trifluroacetic acid gave subarine (37, Scheme 7) [66]. Method B: A second synthesis path of subarine (37

A facile synthetic route to benzimidazolium salts bearing bulky aromatic N-substituents

• Gabriele Grieco,
• Olivier Blacque and
• Heinz Berke

Beilstein J. Org. Chem. 2015, 11, 1656–1666, doi:10.3762/bjoc.11.182

• with the preparation of the N1,N2-di(pyridine-2-yl)benzen-1,2-diamine (8). The Buchwald–Hartwig amination was applied in the syntheses of 5 and 6 where 1,2-dichlorobenzene was coupled with aniline and 2,4,6-trimethylaniline, respectively (Scheme 1). Attempting the synthesis of the N1,N2-bis(2,6

• for 10 min at room temperature. Then 1,2-dichlorobenzene (0.65 mL, 6.67 mmol) was added followed by aniline addition (1.61 mL, 17.32 mmol) and the t-BuONa reagent (1664 mg, 17.32 mmol). An additional amount of toluene (40 mL) was used to rinse the walls of the Schlenk vessel and the solution was then

Fates of imine intermediates in radical cyclizations of N-sulfonylindoles and ene-sulfonamides

• Hanmo Zhang,
• E. Ben Hay,
• Stephen J. Geib and
• Dennis P. Curran

Beilstein J. Org. Chem. 2015, 11, 1649–1655, doi:10.3762/bjoc.11.181

• amination of N-tosylindole aldehyde 6 with 2-iodoaniline (66%), followed by methylation of the aniline nitrogen atom (91%). Substrate 10 with the ester on C2 of the indole was chosen to learn if a more stabilized radical intermediate would still eliminate the N-tosyl group. Reductive amination of 9, 2

• -iodoaniline, PPTS (pyridinium p-toluenesulfonate) and NaBH4 (64%) was followed by N-acylation of the aniline nitrogen atom (80%) provided the target precursor 10. The reaction of 7 with 1 equiv of tributyltin hydride was incomplete, but the use of 2.5 equiv of tributyltin hydride at fixed concentration ([7

• -alkyl (rather than N-aryl) groups are not readily reduced under the same conditions [11]. Cyclizations of aniline derivatives of ene-sulfonamides We next studied cyclizations of several aniline analogs of ene-sulfonamides as summarized in Figure 4. The generic substrate 18 was loosely designed based on

Preparative semiconductor photoredox catalysis: An emerging theme in organic synthesis

• David W. Manley and
• John C. Walton

Beilstein J. Org. Chem. 2015, 11, 1570–1582, doi:10.3762/bjoc.11.173

• case of benzylic amines and piperidine, but aliphatic amines and aniline exhibited poor reactivity. Carboxylic acids are available in great variety from natural and industrial sources. Green synthetic methods based around them as starting materials are undoubtedly worthy of development. That simple

Pyridine-promoted dediazoniation of aryldiazonium tetrafluoroborates: Application to the synthesis of SF₅-substituted phenylboronic esters and iodobenzenes

• George Iakobson,
• Junyi Du,
• Alexandra M. Z. Slawin and
• Petr Beier

Beilstein J. Org. Chem. 2015, 11, 1494–1502, doi:10.3762/bjoc.11.162

• . Starting from aniline derivative 1b, a one pot diazotization–borylation sequence using different acids afforded the corresponding borylated product 2b in good yields (Table 3). Suzuki–Miyaura cross-coupling reactions of boronates 2a and 2b with aryl iodides using a simple system without any optimization

• Sandmeyer reaction starting from SF5-containing aniline derivatives. Finally, hydrodediazoniation of SF5-phenyldiazonium tetrafluoroborates by hydrogen atom abstraction from THF in the presence of pyridine provided (pentafluorosulfanyl)benzene. Borylation of aryldiazonium tetrafluoroborates 3. Reaction

• (3.6 mL), rt, 20 min. Iodination of aryldiazonium tetrafluoroborates 3. Reaction conditions: 3 (1 mmol), I2 (1.1 mmol), pyridine (4 mmol), MeCN (3 mL), 2 h. aYields in the presence of collidine instead of pyridine. Synthesis of boronates 2 from aniline derivatives 1a. Synthesis of diazonium

Azobenzene-based inhibitors of human carbonic anhydrase II

• Leander Simon Runtsch,
• David Michael Barber,
• Peter Mayer,
• Michael Groll,
• Dirk Trauner and
• Johannes Broichhagen

Beilstein J. Org. Chem. 2015, 11, 1129–1135, doi:10.3762/bjoc.11.127

• enzyme affinity. Results and Discussion Azobenzenes can be synthesized by a variety of known chemical transformations [8]. Among them the most widely used is the diazotization of aniline, followed by trapping of the diazonium salt with an electron-rich aromatic compound (such as anilines and phenols

• led to azobenzenes 1a [6], 1b [9] and 1c, in moderate to low yields (43%, 38% and 25%, respectively) (Scheme 1a). Employing methylene-protected aniline 2 (crystal structure depicted in Scheme 1e) according to the procedure from Supuran and co-workers [6], amino azobenzene 1d was isolated after a one

• characterization of azobenzene-containing aryl sulfonamides by different strategies. a) Diazotization and trapping of the diazonium salt with an electron-rich aromatic compound yields azobenzenes 1a–c. b) Reaction of methylene sulfonate-protected aniline and one-pot deprotection yields 1d, which can be converted

Are D-manno-configured Amadori products ligands of the bacterial lectin FimH?

• Tobias-Elias Gloe,
• Insa Stamer,
• Cornelia Hojnik,
• Tanja M. Wrodnigg and
• Thisbe K. Lindhorst

Beilstein J. Org. Chem. 2015, 11, 1096–1104, doi:10.3762/bjoc.11.123

• efficient and versatile approach towards D-manno-configured C-glycosyl-type glycoconjugates. In our study, we have employed two different amines in the Amadori rearrangement with 8, propargylamine and aniline. Under typical conditions for this reaction [2] 1-progargylamino-1-deoxy-D-manno-heptulose 9 and 1

• -phenylamino-1-deoxy-D-manno-heptulose 10 were obtained as pure α-anomers in 77% and 24% yield, respectively (Scheme 3). The low yield of compound 10 may be explained by the low pKa value (4.62) of aniline compared to a pKa of 8.15 for propargylamine, the latter being clearly more efficient as a nucleophile

• for manno-configured C-glycosyl-type hexoses via the Amadori rearrangement was reported. We have employed propargylamine and aniline to prepare 9 and 10, respectively. They carry an anomeric hydroxy group positioned to the α-face of the sugar ring and a rather bulky β-positioned alkyl/aryl aminomethyl

Single-molecule conductance of a chemically modified, π-extended tetrathiafulvalene and its charge-transfer complex with F₄TCNQ

• Raúl García,
• M. Ángeles Herranz,
• Edmund Leary,
• M. Teresa González,
• Gabino Rubio Bollinger,
• Marius Bürkle,
• Linda A. Zotti,
• Yoshihiro Asai,
• Fabian Pauly,
• Juan Carlos Cuevas,
• Nicolás Agraït and
• Nazario Martín

Beilstein J. Org. Chem. 2015, 11, 1068–1078, doi:10.3762/bjoc.11.120

• viologen [5][6], aniline [7][8], thiophene [9], anthraquinone [10] and ferrocene [11] have been previously studied. However, a particularly suitable redox-active molecule for molecular electronics is the well-known electron donor tetrathiafulvalene (TTF) molecule. Pristine TTF, as well as the

Radical-mediated dehydrative preparation of cyclic imides using (NH₄)₂S₂O₈–DMSO: application to the synthesis of vernakalant

• Dnyaneshwar N. Garad,
• Subhash D. Tanpure and
• Santosh B. Mhaske

Beilstein J. Org. Chem. 2015, 11, 1008–1016, doi:10.3762/bjoc.11.113

• studied on varyingly substituted aliphatic/aromatic primary amines and saturated/unsaturated cyclic anhydrides. The generalization of the protocol was first studied on succinic anhydrides and various aromatic amines (Table 2, entries 1–10). The reaction works well with aniline, alkyl-substituted aniline

• and aniline with electron donating or withdrawing substituents at various positions of the aromatic ring (Table 2, entries 1–5). The reaction performed equally well on 1 g scale (Table 2, entry 3). The steric hindrance or electronic factors did not show much effect on the yield of the reaction

• excellent yield (Table 2, entries 11 and 12). Interestingly, the N-phenyl analogue of Captan, a commercially used fungicide could be synthesized in excellent yield (Table 2, entry 12) [18][19]. The reaction of aromatic amines with unsaturated anhydrides to form maleimides was investigated (Table 3). Aniline

Diastereoselective and enantioselective conjugate addition reactions utilizing α,β-unsaturated amides and lactams

• Katherine M. Byrd

Beilstein J. Org. Chem. 2015, 11, 530–562, doi:10.3762/bjoc.11.60

• bisoxazolines for asymmetric aza-Michael additions. For example, Hii and co-workers reported the first example of the use of a palladium(II) complex for the aza-Michael additions of selected α,β-unsaturated N-alkenoyloxazolidinones [237] (Scheme 31). This reaction worked best when aniline was the aromatic amine

• that was used for the addition. Though the use of 4-Cl-C6H4NH2 gave similar results as with the parent compound aniline, the 1,4-addition reaction proceeded in high yield but low enantioselectivity when 4-OMe-C6H4NH2 was used as the nucleophile. This result revealed that these reaction conditions only

• were also able to determine that the aniline competitively binds to the catalyst. In order to avoid deactivation of the catalyst by the free aniline, the authors maintained a low aniline concentration during the reaction by using a syringe pump to add the aniline over 20 hours. Scheme 33 shows the

Synthesis and surface grafting of a β-cyclodextrin dimer facilitating cooperative inclusion of 2,6-ANS

• Lars W. Städe,
• Thorbjørn T. Nielsen,
• Laurent Duroux,
• Reinhard Wimmer,
• Kyoko Shimizu and
• Kim L. Larsen

Beilstein J. Org. Chem. 2015, 11, 514–523, doi:10.3762/bjoc.11.58

• derivatives, 2-(N-methylanilino)naphthalene-6-sulfonic acid (2,6-MANS) and 2-(p-toluidinyl)naphthalene-6-sulfonic acid (2,6 TNS) [23]. These derivatives differ from 2,6-ANS only by having a methyl substitution at the aniline moiety (Figure 2). In the relevant study [23], the formation of a stable 2:1 complex

Multicomponent versus domino reactions: One-pot free-radical synthesis of β-amino-ethers and β-amino-alcohols

• Bianca Rossi,
• Nadia Pastori,
• Simona Prosperini and
• Carlo Punta

Beilstein J. Org. Chem. 2015, 11, 66–73, doi:10.3762/bjoc.11.10

• approach. In fact, our procedure requires neither the preformation of imines nor anhydrous media, due to the coordinating effect of titanium salts, which promote the one-pot synthesis of amino derivatives according to a classical MCR. The basic approach consists of the simple mixing of an aniline, an

Come-back of phenanthridine and phenanthridinium derivatives in the 21st century

• Lidija-Marija Tumir,
• Marijana Radić Stojković and
• Ivo Piantanida

Beilstein J. Org. Chem. 2014, 10, 2930–2954, doi:10.3762/bjoc.10.312

• pyrolysis of the condensation product of benzaldehyde and aniline [6]. The reaction conditions were improved by Morgan and Walls, based on a reaction including a cyclization of phenanthridine by dehydrative ring-closure with phosphorus oxychloride in boiling nitrobenzene [7]. Over the 20th century this

• phenanthridine core starting from a simple disubstituted aniline relied on the aza-Claisen rearrangement, ring-closing enyne metathesis and Diels–Alder reaction [41] (Scheme 18). The obtained phenanthridine derivatives were polysubstituted at the phenyl side-rings, while retaining the unsubstituted central

Synthesis of aromatic glycoconjugates. Building blocks for the construction of combinatorial glycopeptide libraries

• Markus Nörrlinger and
• Thomas Ziegler

Beilstein J. Org. Chem. 2014, 10, 2453–2460, doi:10.3762/bjoc.10.256

• acids; aniline; carbohydrates; glycoconjugates; glycopeptides; Introduction Glycans or other complex oligosaccharide structures, present on the surface of every prokaryotic and eukaryotic cell, are important for a large number of biological recognition processes like, for example, intercellular

Synthesis of α-amino amidines through molecular iodine-catalyzed three-component coupling of isocyanides, aldehydes and amines

• Praveen Reddy Adiyala,
• D. Chandrasekhar,
• Jeevak Sopanrao Kapure,
• Chada Narsimha Reddy and
• Ram Awatar Maurya

Beilstein J. Org. Chem. 2014, 10, 2065–2070, doi:10.3762/bjoc.10.214

• reaction, we carried out a model reaction of tert-butyl isocyanide (1 mmol), benzaldehyde (1 mmol), and aniline (2 mmol) using 5 mol % of molecular iodine in methanol (Table 1). The reaction worked well at ambient temperature and led to good yields of 4a. Among various solvents screened, methanol was found

• mechanism for the iodine-catalyzed α-amino amidine synthesis. Synthesis of α-amino amidine 4a through a three-component coupling of benzaldehyde, aniline, and tert-butyl isocyanide.a Scope of the α-amino amidine synthesis through three-component coupling of aldehyde, amine, and isocyanide.a Supporting

Five-membered ring annelation in [2.2]paracyclophanes by aldol condensation

• Henning Hopf,
• Swaminathan Vijay Narayanan and
• Peter G. Jones

Beilstein J. Org. Chem. 2014, 10, 2021–2026, doi:10.3762/bjoc.10.210

• of the cyclophane framework (endo-orientation) or to the outer section of the derivative (exo-orientation). Thus altogether the six different diastereomers 10–15 result. Results and Discussion As the experiment shows (treatment of 9 with either sodium hydroxide in methanol or aniline in methanol

Multicomponent reactions in nucleoside chemistry

• Mariola Koszytkowska-Stawińska and
• Włodzimierz Buchowicz

Beilstein J. Org. Chem. 2014, 10, 1706–1732, doi:10.3762/bjoc.10.179

• . An example of the application of the Kabachnik–Fields reaction in nucleoside chemistry represents the preparation of α-arylaminophosphonates 28 and 29 by Zhang et al. (Scheme 12) [76]. The reactions between 5-formyl-2'-deoxyuridine 27 (or its 3',5'-di-O-acetyl derivative 14), an aniline and dimethyl

Chemistry of polyhalogenated nitrobutadienes, 14: Efficient synthesis of functionalized (Z)-2-allylidenethiazolidin-4-ones

• Viktor A. Zapol’skii,
• Jan C. Namyslo,
• Mimoza Gjikaj and
• Dieter E. Kaufmann

Beilstein J. Org. Chem. 2014, 10, 1638–1644, doi:10.3762/bjoc.10.170

• ], our approach, starting from a mercaptoacetic acid derivative of perchloro-2-nitro-1,3-butadiene and an aniline, is unprecedented up to now. In this context, it is very interesting that the reaction of a 2-nitro-1-thioperchlorobuta-1,3-diene with N-nucleophiles usually yields a 1-amino-2-nitro-1

• -[4-tolylthio]allylidene)thiazolidin-4-one (19) in 70% yield (Scheme 2). According to proton NMR, the ring-closing step with the parent aniline or with one of its para-substituted derivatives in each case led to a single N-arylthiazolidin-4-one isomer 7–15. In the case of the ortho- or meta

• gives an idea of the abovementioned bulkiness, even in the case of the depicted para-substitution (Figure 2). The formation of the thiazolidin-4-ones 7–18 is assumed to consist of three individual steps. In a SNVin type reaction with the aniline derivative intermediate A (Scheme 3) is formed

Synthesis of new, highly luminescent bis(2,2’-bithiophen-5-yl) substituted 1,3,4-oxadiazole, 1,3,4-thiadiazole and 1,2,4-triazole

• Anastasia S. Kostyuchenko,
• Vyacheslav L.Yurpalov,
• Aleksandra Kurowska,
• Wojciech Domagala,
• Adam Pron and
• Alexander S. Fisyuk

Beilstein J. Org. Chem. 2014, 10, 1596–1602, doi:10.3762/bjoc.10.165

• ) could not be obtained by reacting 11 with O=P(NHPh)3 [30]. The major reaction product was the corresponding oxadiazole derivative 13. An attempt to replace the oxygen atom by the nitrogen one upon refluxing 13 with aniline [31][32] was also unsuccessful. For these reasons, a different approach [33] had

• to be used for the synthesis of 3,5-bis(3-decyl-2,2'-bithiophen-5-yl)-4-phenyl-4H-1,2,4-triazole (18). Anilide 16 was used as a building block for the synthesis of 18. It was prepared from 8 by a consecutive reaction with oxalyl chloride and then aniline. In the next step 16 was converted to 3-decyl