Mechanism, kinetics and selectivity of selenocyclization of 5-alkenylhydantoins: an experimental and computational study

• Biljana M. Šmit,
• Radoslav Z. Pavlović,
• Dejan A. Milenković and
• Zoran S. Marković

Beilstein J. Org. Chem. 2015, 11, 1865–1875, doi:10.3762/bjoc.11.200

• theory (DFT) methods. The pathways of the reaction are investigated in detail. There are two regioselective pathways related to 5-exo and 6-endo products. Theoretical calculations and the monitoring of the cyclization reaction using 1H NMR spectroscopy are in a good agreement with the proposed mechanism

• spectrometer in CD3CN as a solvent. Tetramethylsilane (δ = 0.0 ppm) was used as internal reference and chemical shifts are reported to the nearest 0.01 ppm. 1H NMR measurements of the cyclization reaction of hydantoin 1 (4.7 mg, 0.024 mmol, 1 equiv) with PhSeCl (5.0 mg, 0.026 mmol, 1.1 equiv) in the presence

Recent applications of ring-rearrangement metathesis in organic synthesis

• Sambasivarao Kotha,
• Milind Meshram,
• Priti Khedkar,
• Shaibal Banerjee and
• Deepak Deodhar

Beilstein J. Org. Chem. 2015, 11, 1833–1864, doi:10.3762/bjoc.11.199

• assemble the erythrina skeleton. To this end, they have identified cyclobutene derivative 48 as a useful synthone for RRM. The cyclobutene derivative 46 has been extended via Grignard addition followed by cyclization reaction. Later, cyclobutene derivative 48 was treated with catalyst 1 in the presence of

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

• ), styelsamine B (4), demethyldeoxyamphimedine (9), and subarine (37) was strategically achieved with up to five steps. Synthesis of styelsamine B (4) and cystodytin J (1) The first route showed the total synthesis of styelsamine B via oxidation, Michael addition, condensation and cyclization reaction steps

Design and synthesis of polycyclic sulfones via Diels–Alder reaction and ring-rearrangement metathesis as key steps

• Sambasivarao Kotha and
• Rama Gunta

Beilstein J. Org. Chem. 2015, 11, 1373–1378, doi:10.3762/bjoc.11.148

• methanesulfonyl chloride in the presence of triethylamine as a base to obtain the dimesylate 3 (89%). Next, compound 3 was subjected to a cyclization reaction by treating with sodium sulfide nonahydrate (Na2S·9H2O) using 20% Aliquat® 336 as a phase–transfer catalyst (PTC) to produce the known sulfide 5 (83%) [31

Selected synthetic strategies to cyclophanes

• Sambasivarao Kotha,
• Mukesh E. Shirbhate and
• Gopalkrushna T. Waghule

Beilstein J. Org. Chem. 2015, 11, 1274–1331, doi:10.3762/bjoc.11.142

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

• 1 from succinanilic acid (2), we observed dehydrative cyclization to furnish N-phenylsuccinimide (3) instead of the expected product 1 (Scheme 1). We were curious to find the actual reagents responsible for this serendipitous facile transformation. We found that the cyclization reaction works in the

DBU-promoted carboxylative cyclization of o-hydroxy- and o-acetamidoacetophenone

• Wen-Zhen Zhang,
• Si Liu and
• Xiao-Bing Lu

Beilstein J. Org. Chem. 2015, 11, 906–912, doi:10.3762/bjoc.11.102

• the 2H-chromen-2-one product (Table 2, entries 2 and 4). o-Hydroxyacetophenone bearing electron-donating alkyl and ether groups, or electron-withdrawing fluoro and bromo groups undergoes the carboxylative cyclization reaction smoothly, affording the corresponding 4-butoxy-2H-chromen-2-ones 2b–2f in

• the carboxylative cyclization reaction to furnish the tricyclic product 2h in moderate yield (Table 2, entry 8). With the successful DBU-promoted carboxylative cyclization of o-hydroxyacetophenone at hand, we then extended this strategy to o-acetamidoacetophenone to synthesize 4-hydroxy-2(1H

• )-quinolinone (Table 3). Using 4 equivalents DBU as base in DMSO at 80 °C, o-acetamidoacetophenone (3a) underwent the carboxylative cyclization reaction to provide 3-acetyl-4-methoxy-2(1H)-quinolinones 4a and 5a (Table 3, entry 1). Noteworthy, the acyl group was no longer bound to nitrogen in the product, which

Gold-catalyzed formation of pyrrolo- and indolo-oxazin-1-one derivatives: The key structure of some marine natural products

• Sultan Taskaya,
• Nurettin Menges and
• Metin Balci

Beilstein J. Org. Chem. 2015, 11, 897–905, doi:10.3762/bjoc.11.101

• into 3,4-dihydropyrrolo- and indolo-oxazin-1-one derivatives by a gold(III)-catalyzed cyclization reaction. Some of the products underwent TFA-catalyzed double bond isomerization and some did not. Cyclization reactions in the presence of alcohol catalyzed by Au(I) resulted in the formation of

• atom-economic process using a gold-catalyzed alkyne cyclization reaction as the key step. Pyrrole and indole, bearing one (substituted) propargyl and carboxy group was initially designed as model substrate for the construction of 6 and 7. Gold-catalyzed intramolecular cyclization of enyene carboxylic

• structure 6 or 7 was not formed. After failure of the cyclization reaction of 13 with AuCl3, even in water-free solvents, we turned our attention to the construction of the pyrrolo-oxazin-1-one skeleton with the corresponding acid 15. For this purpose, the propargyl ester 13 was first hydrolyzed with K2CO3

Direct access to pyrido/pyrrolo[2,1-b]quinazolin-9(1H)-ones through silver-mediated intramolecular alkyne hydroamination reactions

• Hengshuai Wang,
• Shengchao Jiao,
• Kerong Chen,
• Xu Zhang,
• Linxiang Zhao,
• Dan Liu,
• Yu Zhou and
• Hong Liu

Beilstein J. Org. Chem. 2015, 11, 416–424, doi:10.3762/bjoc.11.47

• in a sealed tube under argon protection at 80 °C for 3 h (Table 1, entry 3). To evaluate the scope of the proposed silver-catalyzed intramolecular hydroamination cyclization reaction, we investigated its tolerance by probing changes in the substituted 2-(4-pentynyl)-4(3H)-quinazolinone (6A) under the

• cyclization reaction, and the expected products 9A–L were obtained in good to excellent yields (80–93%, Table 3, entries 1–12). Based on the results of the present studies, we propose a plausible mechanism for the transformation. As depicted in Scheme 2, the intramolecular cyclization is initiated by the

• through an AgOTf-catalyzed intramolecular alkyne hydroamination cyclization reaction. The methodology is applicable to a wide scope of substrates and generates a series of fused quinazolinone heterocycles in good to excellent yields. It lends itself an alternative method to the construction of innovative

Azirinium ylides from α-diazoketones and 2H-azirines on the route to 2H-1,4-oxazines: three-membered ring opening vs 1,5-cyclization

• Nikolai V. Rostovskii,
• Mikhail S. Novikov,
• Alexander F. Khlebnikov,
• Galina L. Starova and
• Margarita S. Avdontseva

Beilstein J. Org. Chem. 2015, 11, 302–312, doi:10.3762/bjoc.11.35

• -azabuta-1,3-dienes which transform back to the oxazines in the dark at room temperature. The rate of the reverse cyclization reaction increases with increasing electron-withdrawing ability of C1-substituent in 2-azabuta-1,3-diene. X-ray crystal structure of azadiene 3e. X-ray crystal structures of

Recent advances in the electrochemical construction of heterocycles

• Robert Francke

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

• order to obtain reasonable reaction rates. When the radical cation is trapped with a hydroxy group, the use of 2,6-lutidine is sufficient. However, a stronger base such as NaOMe is needed when tosylamines are converted in order to facilitate the cyclization reaction and to suppress intermolecular

• their approach, unsaturated and saturated carboxylic acids were simultaneously subjected to a mixed Kolbe-type oxidation in a KOH/methanol electrolyte using an undivided cell under galvanostatic conditions (Scheme 7). The cyclization reaction is initiated with the generation of radical 17 upon anodic

• . However, Okimoto et al. could recently demonstrate that iminium species can be generated selectively and used for a cyclization reaction when a stabilizing benzyl group is attached to the nitrogen (Scheme 12, compound 29) [55]. The hydroxy group tethered to the substrate serves for nucleophilic trapping

Preparation of neuroprotective condensed 1,4-benzoxazepines by regio- and diastereoselective domino Knoevenagel–[1,5]-hydride shift cyclization reaction

• László Tóth,
• Yan Fu,
• Hai Yan Zhang,
• Attila Mándi,
• Katalin E. Kövér,
• Tünde-Zita Illyés,
• Attila Kiss-Szikszai,
• Balázs Balogh,
• Tibor Kurtán,
• Sándor Antus and
• Péter Mátyus

Beilstein J. Org. Chem. 2014, 10, 2594–2602, doi:10.3762/bjoc.10.272

• Knoevenagel–[1,5]-hydride shift cyclization reaction of a 4-aryl-2-phenyl-1,4-benzoxazepine derivative obtained from flavanone. The relative configuration of products were determined by the correlation of 3JH,H coupling data with the geometry of major conformers accessed by DFT conformational analysis

• neuroprotective condensed 2-phenyl-1,4-benzoxazepines rac-7a,b through the diastereoselective domino Knoevenagel–1,5-hydride shift cyclization reaction rac-5→rac-7a,b from the readily available 4-aryl-2-phenyl-1,4-benzoxazepine derivative, rac-5 (Scheme 1). Ring-closure transformations involving C(sp3)–H bond

• ] or organocatalytic [16][17] reactions and the mechanism of the stereospecific hydride transfer have been recently studied by several research groups. The synthetic potential of the diastereoselective domino Knoevenagel–[1,5]-hydride shift cyclization reaction was exploited in our present work for the

A small azide-modified thiazole-based reporter molecule for fluorescence and mass spectrometric detection

• Stefanie Wolfram,
• Hendryk Würfel,
• Stefanie H. Habenicht,
• Christine Lembke,
• Phillipp Richter,
• Eckhard Birckner,
• Rainer Beckert and
• Georg Pohnert

Beilstein J. Org. Chem. 2014, 10, 2470–2479, doi:10.3762/bjoc.10.258

• synthesis of the azide-bearing fluorophore starts with a Hantzsch thiazole formation employing pyridine-2-carbothioamide (2) and ethyl 2-bromo-2-(4-bromophenyl)acetate (3) (Scheme 1). The cyclization reaction leads, under basic catalysis in moderate yield (ca. 50%), to 5-(4-bromophenyl)-2-(pyridin-2-yl

Synthesis of 2-trifluoromethylpyrazolo[5,1-a]isoquinolines via silver triflate-catalyzed or electrophile-mediated one-pot tandem reaction

• Xiaoli Zhou,
• Meiling Liu,
• Puying Luo,
• Yingjun Lai,
• Tangtao Yang and
• Qiuping Ding

Beilstein J. Org. Chem. 2014, 10, 2286–2292, doi:10.3762/bjoc.10.238

• 1i reacted with 2, leading to the desired pyrazolo[5,1-a]isoquinoline 3i in 90% yield (Table 2, entry 9). Subsequently, based on our previous reports on electrophile-mediated electrophilic cyclization reaction [28][29], one-pot tandem electrophilic cyclization/[3 + 2] cycloaddition of N’-(2

Derivatives of the triaminoguanidinium ion, 3. Multiple N-functionalization of the triaminoguanidinium ion with isocyanates and isothiocyanates

• Jan Szabo,
• Kerstin Karger,
• Nicolas Bucher and
• Gerhard Maas

Beilstein J. Org. Chem. 2014, 10, 2255–2262, doi:10.3762/bjoc.10.234

• (benzylamino)guanidinium chloride and aryl isothiocyanates. Here, a cyclization reaction occurred after thiocarbamoylation of the first NH2 group. The diverse reaction routes reported in this paper nicely demonstrate the versatility of TAG-derived 1,2,3-tris(alkylamino)guanidinium ions respect to synthetic

Magnesium bis(monoperoxyphthalate) hexahydrate as mild and efficient oxidant for the synthesis of selenones

• Andrea Temperini,
• Massimo Curini,
• Ornelio Rosati and
• Lucio Minuti

Beilstein J. Org. Chem. 2014, 10, 1267–1271, doi:10.3762/bjoc.10.127

• the oxidative-cyclization reaction of 1j not only favoured the oxidation reaction, but also suppressed the β-elimination side reaction of the selenoxide intermediate [14]. Thus tetrahydrofuran 3j was obtained in 69% yield (Table 2, entry 7) as the sole product. It is interesting to note that N

Atherton–Todd reaction: mechanism, scope and applications

• Stéphanie S. Le Corre,
• Mathieu Berchel,
• Hélène Couthon-Gourvès,
• Jean-Pierre Haelters and
• Paul-Alain Jaffrès

Beilstein J. Org. Chem. 2014, 10, 1166–1196, doi:10.3762/bjoc.10.117

• expected phosphoramidate was jointly isolated with 5 to 10% of thiophosphoramidate resulting from a cyclization reaction. The chiral phosphoramidates (Scheme 32-ii and iii) were tested as a chiral catalyst for the nucleophilic addition of diethylzinc [107] on benzaldehyde or for the asymmetric borane

Theoretical studies on the intramolecular cyclization of 2,4,6-t-Bu₃C₆H₂P=C: and effects of conjugation between the P=C and aromatic moieties

• Masaaki Yoshifuji and
• Shigekazu Ito

Beilstein J. Org. Chem. 2014, 10, 1032–1036, doi:10.3762/bjoc.10.103

• [10][14]. As an alternative reaction of phosphanylidenecarbenoid, we have previously found the intramolecular cyclization reaction affording 6,8-di-tert-butyl-3,4-dihydro-4,4-dimethyl-1-phosphanaphthalene (2) putatively through formation of phosphanylidenecarbene 1 generated from Mes*P=C(Br)Li (Scheme

Allenylphosphine oxides as simple scaffolds for phosphinoylindoles and phosphinoylisocoumarins

• G. Gangadhararao,
• Ramesh Kotikalapudi,
• M. Nagarjuna Reddy and
• K. C. Kumara Swamy

Beilstein J. Org. Chem. 2014, 10, 996–1005, doi:10.3762/bjoc.10.99

• , over the last decade, allenes have attained a prominent position in organic transformations like cycloaddition, cycloisomerization, base or metal-catalyzed reactions [5][6][7]. In particular, cyclization reaction of allenes has emerged as a valuable tool in developing different methods leading to

On the mechanism of photocatalytic reactions with eosin Y

• Michal Majek,
• Fabiana Filace and
• Axel Jacobi von Wangelin

Beilstein J. Org. Chem. 2014, 10, 981–989, doi:10.3762/bjoc.10.97

• phenanthrene synthesis [19]. A solution of o-biphenyldiazonium tetrafluoroborate in acetonitrile showed strong absorption between 400–500 nm with all light at the UV–vis edge at 400 nm being completely absorbed. This again indicates that direct photocleavage of the C–N bond might be operating. The cyclization

• reaction with ethyl propiolate according to the literature protocol [19] but in the absence of eosin Y did not afford any phenanthrene product (Scheme 5). Instead, a Ritter-type reaction proceeded to give the corresponding acetanilide after aqueous work-up which is consistent with the original report by

Site-selective covalent functionalization at interior carbon atoms and on the rim of circumtrindene, a C₃₆H₁₂ open geodesic polyarene

• Hee Yeon Cho,
• Ronald B. M. Ansems and
• Lawrence T. Scott

Beilstein J. Org. Chem. 2014, 10, 956–968, doi:10.3762/bjoc.10.94

• -trichlorodecacyclene (12) by FVP at 1100 °C (Scheme 3) [20]. The importance of strategically functionalizing hydrocarbon precursors in a way that will generate radical centers where new bonds are to be formed by FVP is dramatically illustrated by the vastly improved efficiency of this triple cyclization reaction when

The influence of intraannular templates on the liquid crystallinity of shape-persistent macrocycles

• Joscha Vollmeyer,
• Ute Baumeister and
• Sigurd Höger

Beilstein J. Org. Chem. 2014, 10, 910–920, doi:10.3762/bjoc.10.89

• templates of being robust against solvent or temperature changes and will still be applicable at elevated temperatures. The bisacetylenes can be prepared independently and attached to the template just prior to the cyclization reaction or, and this is done here, the (template bound) oligoacetylene is

• oligoether template crosses the ring, no lc behavior is observed. In both cases an induced non-planarity of the macrocycles is assumed. Shape-persistent macrocycles with different peripheral side groups and intraannular templates. GPC elugrams of the crude product of the cyclization reaction of 1a (—) and 1d

Aza-Diels–Alder reaction between N-aryl-1-oxo-1H-isoindolium ions and tert-enamides: Steric effects on reaction outcome

• Amitabh Jha,
• Ting-Yi Chou,
• Zainab ALJaroudi,
• Bobby D. Ellis and
• T. Stanley Cameron

Beilstein J. Org. Chem. 2014, 10, 848–857, doi:10.3762/bjoc.10.81

• the N-aryl group undergo intramolecular electrophilic addition to the alkene yielding isoindolo[2,1-a]quinolines under acidic conditions [18]. Isoindolo[2,1-a]quinolone cores have also been prepared via an aldol-type intramolecular cyclization reaction of N-(2-acetylaryl)phthalimide under anhydrous

First synthesis of meso-substituted pyrrolo[1,2-a]quinoxalinoporphyrins

• Dileep Kumar Singh and
• Mahendra Nath

Beilstein J. Org. Chem. 2014, 10, 808–813, doi:10.3762/bjoc.10.76

• synthesis of novel meso-substituted pyrrolo[1,2-a]quinoxalinoporphyrins (4a–h) began via the Pictet–Spengler cyclization reaction [50][51] of 5-(3-amino-4-(pyrrol-1-yl)phenyl)-10,15,20-triphenylporphyrin (3) with various aromatic aldehydes by using 2% TFA in dichloromethane as an acidic catalyst at 0 °C for

Isocyanide-based multicomponent reactions towards cyclic constrained peptidomimetics

• Gijs Koopmanschap,
• Eelco Ruijter and
• Romano V.A. Orru

Beilstein J. Org. Chem. 2014, 10, 544–598, doi:10.3762/bjoc.10.50