Molecular iodine-catalyzed one-pot multicomponent synthesis of 5-amino-4-(arylselanyl)-1H-pyrazoles

• Camila S. Pires,
• Daniela H. de Oliveira,
• Maria R. B. Pontel,
• Jean C. Kazmierczak,
• Roberta Cargnelutti,
• Diego Alves,
• Raquel G. Jacob and
• Ricardo F. Schumacher

Beilstein J. Org. Chem. 2018, 14, 2789–2798, doi:10.3762/bjoc.14.256

• Lewis acid to generate the hydrazone intermediate A. Then, hydrazone A undergoes a cyclization reaction followed by an oxidative aromatization to yield 1H-pyrazol-5-amine 5. At the same time, the diaryl diselenide 3 reacts with the molecular iodine to generate an electrophilic selenium species B. The

An overview on recent advances in the synthesis of sulfonated organic materials, sulfonated silica materials, and sulfonated carbon materials and their catalytic applications in chemical processes

• Hashem Sharghi,
• Pezhman Shiri and
• Mahdi Aberi

Beilstein J. Org. Chem. 2018, 14, 2745–2770, doi:10.3762/bjoc.14.253

• another published article by this research group, silica-supported sulfonated 1,4-diazabicyclo[2.2.2]octane 71 was used for the one-pot tandem Knoevenagel–Michael cyclization reaction between isatin derivatives 32 or acenaphthenquinone (33), barbituric acid derivatives 73, and 1,3-dicarbonyl compounds 20

Synthesis of dihydroquinazolines from 2-aminobenzylamine: N³-aryl derivatives with electron-withdrawing groups

• Nadia Gruber,
• Jimena E. Díaz and
• Liliana R. Orelli

Beilstein J. Org. Chem. 2018, 14, 2510–2519, doi:10.3762/bjoc.14.227

• ’-diacylation products were observed due to the low nucleophilicity of the secondary amino group, bearing a deactivating aromatic ring and all desired compounds were obtained with excellent yields (Table 2). Then, the microwave-assisted cyclization reaction leading to 3,4-dihydroquinazolines 1 was initially

Synthesis of a leopolic acid-inspired tetramic acid with antimicrobial activity against multidrug-resistant bacteria

• Luce Mattio,
• Loana Musso,
• Leonardo Scaglioni,
• Andrea Pinto,
• Piera Anna Martino and
• Sabrina Dallavalle

Beilstein J. Org. Chem. 2018, 14, 2482–2487, doi:10.3762/bjoc.14.224

• , is an imperative goal to stay ahead of the evolution of antibiotic resistance. Herein we report the synthesis of a 3-decyltetramic acid analogue of the ureido dipeptide natural antibiotic leopolic acid A. The key step in the synthetic strategy is an intramolecular Lacey–Dieckmann cyclization reaction

• obtain compound 9 in 90% yield. As expected, the cyclization reaction was found to be quite troublesome. Several attempts were made using different conditions (TBAF, Et2O, rt; NaOEt, EtOH, reflux; NaH, THF, reflux; LDA, THF, −78 °C), but they all were unsuccessful. Finally, we succeeded in preparing

Microfluidic light-driven synthesis of tetracyclic molecular architectures

• Javier Mateos,
• Nicholas Meneghini,
• Marcella Bonchio,
• Nadia Marino,
• Tommaso Carofiglio,
• Xavier Companyó and
• Luca Dell’Amico

Beilstein J. Org. Chem. 2018, 14, 2418–2424, doi:10.3762/bjoc.14.219

• or 5. Generality and limits of the light-driven [4 + 2] cyclization reaction between 2-MBP 1a–g and coumarins 2a–c under MFP setup. *Residence time was 60 min. Generality and limits of the light-driven [4 + 2] cyclization reaction between 2-MBP 1a–f and chromone (3a) under MFP setup. MFP parallel

Nucleoside macrocycles formed by intramolecular click reaction: efficient cyclization of pyrimidine nucleosides decorated with 5'-azido residues and 5-octadiynyl side chains

• Jiang Liu,
• Peter Leonard,
• Sebastian L. Müller,
• Constantin Daniliuc and
• Frank Seela

Beilstein J. Org. Chem. 2018, 14, 2404–2410, doi:10.3762/bjoc.14.217

• derivative 4 the dU macrocycle 8 could be isolated in 46% yield even in the absence of TBTA. However, the yield of cyclization was significantly improved when TBTA was added (69%). This demonstrates the influence of the nucleobase on the intramolecular cyclization reaction. All compounds were characterized

• derivatives 4 and 8, resulted in high cyclization yields (around 70%) without formation of dimeric or oligomeric molecules. The speed of the TBTA catalyzed click reaction and dilution (Ruggli–Ziegler dilution principle) [43] can be made responsible for this behavior. For the copper(I)-promoted cyclization

• reaction the use of the TBTA complex was essential for the cyclization of dC precursor 2 but not for dU precursor 7. Protection of precursor molecules is not required and only four steps are necessary to convert a nucleoside in a nucleoside macrocycle. The single crystal X-ray structure confirmed the click

Synthesis of spirocyclic scaffolds using hypervalent iodine reagents

• Fateh V. Singh,
• Priyanka B. Kole,
• Saeesh R. Mangaonkar and
• Samata E. Shetgaonkar

Beilstein J. Org. Chem. 2018, 14, 1778–1805, doi:10.3762/bjoc.14.152

• ) for spirocyclization of N-protected tyrosine 14 to spirolactone 16. The spirocyclization reaction was carried out in methanol using stoichiometric amounts of PIDA (15) and spirolactone 16 was isolated in 35% yield (Scheme 2). Probably, the cyclization reaction proceeded via dearomatizaion of phenolic

• bond formation using 10 mol % of iodotoluene 33 as precatalyst, 1.0 equivalent of CF3COOH as an additive and mCPBA as terminal oxidant in trifluoroethanol (Scheme 26). The spirocyclic compounds 77 were isolated in high yields. The cyclization reaction was probably initiated by in situ generated active

• substrates and polymer-supported hypervalent iodine reagent was used in one step. In this report, p-substituted phenolic compound 131 was cyclized to spirocyclic compound 133 in 50% yield containing a seven membered ring system. The cyclization reaction was carried out using polymer-supported PIFA reagent

Synthesis of chiral 3-substituted 3-amino-2-oxindoles through enantioselective catalytic nucleophilic additions to isatin imines

• Hélène Pellissier

Beilstein J. Org. Chem. 2018, 14, 1349–1369, doi:10.3762/bjoc.14.114

• cinchona alkaloid-derived thiourea. Aza-Henry reaction of N-Boc-isatin imines with nitromethane catalyzed by a bifunctional guanidine. Domino addition/cyclization reaction of N-Boc-isatin imines with 1,4-dithiane-2,5-diol (53) catalyzed by a tertiary amine-squaramide. Nickel-catalyzed additions of methanol

One hundred years of benzotropone chemistry

• Arif Dastan,
• Haydar Kilic and
• Nurullah Saracoglu

Beilstein J. Org. Chem. 2018, 14, 1120–1180, doi:10.3762/bjoc.14.98

• -benzotropone (11) with dimethyl barbituric acid (62) and subsequent oxidative cyclization reaction using DDQ-Sc(OTf)3 or photoirradiation under aerobic conditions afforded 61+.BF4− (Scheme 12). The pKR+ value and reduction potential of the cation 61 were studied. The relative stability of a carbocation can be

Methyl isocyanide as a convertible functional group for the synthesis of spirocyclic oxindole γ-lactams via post-Ugi-4CR/transamidation/cyclization in a one-pot, three-step sequence

• Amarendar Reddy Maddirala and
• Peter R. Andreana

Beilstein J. Org. Chem. 2018, 14, 875–883, doi:10.3762/bjoc.14.74

• analysis (Figure 1). We then elected to carry out yield optimization studies of the cyclization reaction using a number of solvents, reagents and reaction temperatures (Table 1) and also to explore the possibility of a possible 4-exo-dig outcome. The study validated that all the reaction conditions, with

• spirocyclic 2-oxindoles. Post-Ugi-4CR/transamidation/cyclization sequence. Base-promoted intramolecular 5-endo-dig cyclization. Reaction scope with varying combinations of substrates. Synthesis of 5-chloro-1'-phenylspiro[indoline-3,2'-pyrrolidine]-2,5'-dione (8a). Method applicability for the one-pot

Recent developments in the asymmetric Reformatsky-type reaction

• Hélène Pellissier

Beilstein J. Org. Chem. 2018, 14, 325–344, doi:10.3762/bjoc.14.21

• (Scheme 23). As an extension of the precedent methodology, the same ligand (1R,2S)-59 was applied to promote the enantioselective domino aza-Reformatsky/cyclization reaction of aromatic imines 60a–h with ethyl bromodifluoroacetate (26) [48]. In this case, a stoichiometric amount of this ligand was

• halofluoroacetate. When the opposite enantiomer of the ligand (1S,2R)-59 was used under the same reaction conditions, it provided the corresponding (3R,4S) product 62a in 70% yield and 90% ee starting from the corresponding imine 60a (Scheme 23). Unfortunately, the scope of this domino Reformatsky/cyclization

• reaction could not be extended to aliphatic imines since they led to complex mixtures. To explain the stereoselectivity of the reaction providing (3S,4R)-62a, the authors proposed transition state K arisen from coordination between zinc ions and imine nitrogen, ligand 59, and the Reformatsky reagent

One-pot sequential synthesis of tetrasubstituted thiophenes via sulfur ylide-like intermediates

• Jun Ki Kim,
• Hwan Jung Lim,
• Kyung Chae Jeong and
• Seong Jun Park

Beilstein J. Org. Chem. 2018, 14, 243–252, doi:10.3762/bjoc.14.16

• yield (32%). Starting from malonitrile, compound 8an was also prepared in a moderate yield (50%) via a Thorpe–Ziegler-type cyclization of N,S-acetal 7an. In this case, the intramolecular cyclization reaction was carried out at 100 °C for 3 h. With 5,5-dimethylcyclohexane-1,3-dione, thiophene 8ao was

Fluorescent nucleobase analogues for base–base FRET in nucleic acids: synthesis, photophysics and applications

• Mattias Bood,
• Sangamesh Sarangamath,
• Moa S. Wranne,
• Morten Grøtli and
• L. Marcus Wilhelmsson

Beilstein J. Org. Chem. 2018, 14, 114–129, doi:10.3762/bjoc.14.7

• decay from excited states via non-radiative processes, in 2012 we decided to re-synthesize the quadracyclic adenine according to the procedure of Buhr et al. (Scheme 8) [51][53]. However, in our hands the vital cyclization reaction starting from compound 36 (Scheme 8) never provided more than a 46

Photocatalytic formation of carbon–sulfur bonds

• Alexander Wimmer and
• Burkhard König

Beilstein J. Org. Chem. 2018, 14, 54–83, doi:10.3762/bjoc.14.4

• metal-free method for the synthesis of benzothiophenes via a photocatalyzed tandem addition/cyclization reaction (Scheme 11) [41]. Aryl thiols were coupled with dimethyl acetylenedicarboxylate, applying 9-mesityl-10-methylacridinium perchlorate (Acr+-Mes ClO4−) as organic photocatalyst and benzoic acid

• N2) which triggers an intramolecular cyclization reaction via a nitrogen-centred radical intermediate to form sulfonylated phenanthridines. The reaction is photocatalyzed by [Ru(bpy)3]Cl2 under irradiation with blue LEDs and proceeds smoothly for a variety of substituted vinyl azides and sulfonyl

Dialkyl dicyanofumarates and dicyanomaleates as versatile building blocks for synthetic organic chemistry and mechanistic studies

• Grzegorz Mlostoń and
• Heinz Heimgartner

Beilstein J. Org. Chem. 2017, 13, 2235–2251, doi:10.3762/bjoc.13.221

• hydrazide, in the presence of ethanol, undergoes a cyclization reaction yielding the aminopyrazole 65 in 44% yield [63] (Scheme 21). The explanation of the reaction course is based on the assumption that under the reaction conditions ethanolysis of the carbohydrazide occurs and the formed enehydrazine 61

Sustainable synthesis of 3-substituted phthalides via a catalytic one-pot cascade strategy from 2-formylbenzoic acid with β-keto acids in glycerol

• Lina Jia and
• Fuzhong Han

Beilstein J. Org. Chem. 2017, 13, 1425–1429, doi:10.3762/bjoc.13.139

• /cyclization reaction of 2-formylbenzoic acid and substituted ketones catalyzed by strong acids [15][16][17], strong bases [18][19] and solid acid catalysts [20][21]. The majority of these protocols generally suffer from one or more drawbacks, such as the requirement of stoichiometric or excess amounts of

• species and glycerol as a solvent will allow the establishment of an efficient catalytic one-pot cascade aldol/cyclization reaction. Herein, we present a new method to provide a convenient, green and efficient alternative for rapidly accessing a variety of 3-substituted phthalides (Scheme 1). Results and

An eco-compatible strategy for the diversity-oriented synthesis of macrocycles exploiting carbohydrate-derived building blocks

• Sushil K. Maurya and
• Rohit Rana

Beilstein J. Org. Chem. 2017, 13, 1106–1118, doi:10.3762/bjoc.13.110

• blocks were coupled via 1,3-dipolar cycloaddition (click reaction) iteratively through the development of a greener base-free Cu(I)-catalyzed azide–alkyne cycloaddition reaction. The cycloadducts were then converted to macrocycles by Ru-catalyzed cyclization reaction using greener and non-hazards

• inherent properties including stability towards acid–base hydrolysis, active participation in H-bonding, dipole–dipole and π-stacking interactions [37][64][65][66]. The reaction would then afford a range of acyclic precursors, which could then undergo the intramolecular cyclization reaction to furnish the

Transition-metal-free one-pot synthesis of alkynyl selenides from terminal alkynes under aerobic and sustainable conditions

• Adrián A. Heredia and
• Alicia B. Peñéñory

Beilstein J. Org. Chem. 2017, 13, 910–918, doi:10.3762/bjoc.13.92

• excess and the correct arrangement and electronic properties of both the amine and alkynyl groups promote a spontaneous cyclization reaction to form indole 9 in good yields [50]. Conclusion We have developed a novel one-pot procedure for the synthesis of alkyl alkynyl selenides in moderate to good yields

Nucleophilic and electrophilic cyclization of N-alkyne-substituted pyrrole derivatives: Synthesis of pyrrolopyrazinone, pyrrolotriazinone, and pyrrolooxazinone moieties

• Işıl Yenice,
• Sinan Basceken and
• Metin Balci

Beilstein J. Org. Chem. 2017, 13, 825–834, doi:10.3762/bjoc.13.83

• pyrrole ring and the imine double bond. With these encouraging results in hand, we embarked on the evaluation of the substrate scope for this useful transformation. The compounds 7a, 7b, and 7d were submitted to a cyclization reaction under the same reaction conditions applied to compound 7c. As shown in

• Scheme 2, compounds 7a and 7d formed 2-aminopyrrolopyrazinone derivatives 12a and 12d, whereas 7b furnished pyrrolotriazinone derivative 13b. The electronic nature of the substituents attached to the alkyne determines the mode of the cyclization reaction. Since the electron-donating methoxy group

• to afford pyrrolotriazinone moiety 13. After completion of the nucleophilic cyclization reactions, we desired to activate the triple bond with iodine to synthesize pyrrolooxazinone derivatives via an electrophilic intramolecular cyclization reaction. For this purpose, N-alkyne-substituted methyl 1H

A practical and efficient approach to imidazo[1,2-a]pyridine-fused isoquinolines through the post-GBB transformation strategy

• Taofeng Shao,
• Zhiming Gong,
• Tianyi Su,
• Wei Hao and
• Chao Che

Beilstein J. Org. Chem. 2017, 13, 817–824, doi:10.3762/bjoc.13.82

• acetylene unit may then undergo a sequential 6-exo-dig cyclization/retro-ene reaction to form the desired imidazo[1,2-a]pyridine-fused isoquinoline 6a. The cyclization reaction could be realized with the aid of silver or gold catalysts [51][52]. With this idea in mind, we commenced our studies by

• detected under these mild conditions. Subsequent heating of 4a in refluxing 1,4-dioxane or toluene failed to deliver the expected product 6a, even under acidic or basic conditions. Then, we turned to Ag and Au catalysts and investigated the metal-catalyzed intramolecular cyclization reaction of 4a and the

• product was obtained in refluxing CH3CN or 1,4-dioxane (Table 1, entries 1–4). It revealed that the solvent plays a key role in this cyclization reaction. For comparison, we tested also AgSbF6 as the catalyst and it was found to be less effective than AgOTf (Table 1, entry 5). To improve the reaction

N-Propargylamines: versatile building blocks in the construction of thiazole cores

• S. Arshadi,
• E. Vessally,
• L. Edjlali,
• R. Hosseinzadeh-Khanmiri and
• E. Ghorbani-Kalhor

Beilstein J. Org. Chem. 2017, 13, 625–638, doi:10.3762/bjoc.13.61

• syntheses of a series of multiply substituted thiazolidines 33 via the cyclization reaction of secondary N-propargylamines 32 with blocked N-isothiocyanate precursors 31. The desired N-isocyanates A are produced in situ upon heating or treatment with a base, in acetonitrile under microwave irradiation

• converted to the corresponding vinylthiazolines 38 through the treatment with dithioic acids 37 in the presence of EDCI in dichloromethane. This transformation is believed to occur through a tandem coupling–cyclization reaction. The authors showed that the treatment of 38 with DBU at 0 °C provided thiazoles

Synthesis of 1-indanones with a broad range of biological activity

• Marika Turek,
• Dorota Szczęsna,
• Marek Koprowski and
• Piotr Bałczewski

Beilstein J. Org. Chem. 2017, 13, 451–494, doi:10.3762/bjoc.13.48

• the carbonylative cyclization reaction of carboxylic acid methyl and ethyl esters 42 which led to the formation of 1-indanones 43 [33]. This reaction was carried out in acetonitrile, in the presence of triethylamine, under carbon monoxide atmosphere, achieving efficiency in the range of 88–92%, when

• 83. The latter underwent a Michael cyclization reaction to afford 84. Finally, dehydratation of 84 gave the spiro bis-indane product 85 (Scheme 27). A new method to synthesize 2-benzylidene-1-indanone derivatives 88a–d has been proposed in 2014 by Álvarez-Toledano et al. [52]. These derivatives were

Brønsted acid-mediated cyclization–dehydrosulfonylation/reduction sequences: An easy access to pyrazinoisoquinolines and pyridopyrazines

• Ramana Sreenivasa Rao and
• Chinnasamy Ramaraj Ramanathan

Beilstein J. Org. Chem. 2017, 13, 428–440, doi:10.3762/bjoc.13.46

• the cyclization reaction in the presence of TfOH at room temperature to generate a potential precursor for the synthesis of praziquantel. To realize the cyclization, the imide 7h was treated with TfOH under neat conditions at 70 °C, quite unfortunately to witness the decomposition of imide 7h. This

• the potassium salt of N-benzyliminodiacetic acid in THF at reflux to furnish the expected imides 8a–c, 8h, and 8i in good yields (Scheme 6). The imide 8h was subjected to the cyclization reaction conditions using 6 equivalents of TfOH under neat conditions at 70 °C followed by reduction using NaBH4

• pyrazinoisoquinolines, 2-oxopiperazines and aldose reductase inhibitors (ALR2). HRMS spectra of aliquot generated from cyclization reaction of 7c. ORTEP diagrams of compound 9b and 10a. Comparison of previous reports with present work for piperazine-2,6-dione synthesis. Coupling of N-benzenesulfonyliminodiacetic acid

The reductive decyanation reaction: an overview and recent developments

• Jean-Marc R. Mattalia

Beilstein J. Org. Chem. 2017, 13, 267–284, doi:10.3762/bjoc.13.30

• decyanation in metal dissolving conditions coupled with deprotection [30]. TBDMS = tert-butyldimethylsilyl. Preparation of α,ω-dienes [18][33]. Cyclization reaction using a radical probe [18]. Synthesis of (±)-xanthorrhizol (8) [39]. Mechanism for the reduction of α-aminonitriles by hydride donors. Synthesis

Regiochemistry of cyclocondensation reactions in the synthesis of polyazaheterocycles

• Patrick T. Campos,
• Leticia V. Rodrigues,
• Andrei L. Belladona,
• Caroline R. Bender,
• Juliana S. Bitencurt,
• Fernanda A. Rosa,
• Davi F. Back,
• Helio G. Bonacorso,
• Nilo Zanatta,
• Clarissa P. Frizzo and
• Marcos A. P. Martins

Beilstein J. Org. Chem. 2017, 13, 257–266, doi:10.3762/bjoc.13.29

• , thiophene-2-glyoxylic acid, and N-(2-amino-4-nitrophenyl)acetamide, in accordance with the mechanism proposed in this work. To rationalize why the cyclization reaction between the amidines 8g,h and the α-ketoester did not occur, the HOMO coefficient and charge densities for the nitrogens of the amidine were