Ultrasound-assisted one-pot green synthesis of new N- substituted-5-arylidene-thiazolidine-2,4-dione-isoxazoline derivatives using NaCl/Oxone/Na3PO4 in aqueous media

A rapid and green method for the synthesis of novel N-thiazolidine-2,4-dione isoxazoline derivatives 5 from N-allyl-5-arylidenethiazolidine-2,4-diones 3 as dipolarophiles with arylnitrile oxides via 1,3-dipolar cycloaddition reaction. The corresponding N-allyl substituted dipolarophiles were prepared by one-pot method from thiazolidine-2,4-dione with aldehydes using Knoevenagel condensation followed by N-allylation of thiazolidine-2,4-dione in NaOH aqueous solution under sonication. In addition, the isoxazoline derivatives 5 were synthesized by regioselective and chemoselective 1,3-dipolar cycloaddition using inexpensive and mild NaCl/Oxone/Na₃PO₄ as a Cl source, oxidant and/or catalyst under ultrasonic irradiation in EtOH/H₂O (v/v, 2:1) as green solvent. All synthesized products are furnished in good yields in the short reaction time, and then their structures were confirmed by NMR, mass spectrometry and X-ray crystallography analysis.     

Reaction of 1,3-cyclohexadiene with the Ge(100) surface

The adsorption and reaction of 1,3-cyclohexadiene with the Ge(100)-(2×1) surface are investigated. The possibility of a surface Diels–Alder reaction ([4+2] cycloaddition), as well as a [2+2] cycloaddition reaction are explored. The surface reactions are followed by ultraviolet photoelectron and high-resolution electron energy loss spectroscopies. The vibrational spectroscopy results are compared with theoretically predicted frequencies for each of the possible surface reactions.     

Thermal reaction of electron deficient 4‐oxo‐4H‐pyrazole 1,2‐dioxide with cycloheptatriene: the first examples of the formation of an endo‐[4π + 6π]‐cycloadduct and an intramolecular 1,3‐dipolar reaction leading to a heterocage

The reaction of 3,5‐bis(methoxycarbonyl)‐4‐oxo‐4H‐pyrazole 1,2‐dioxide (1a) with 1,3,5‐cycloheptatriene (2b) gave a mixture of the novel endo‐[4 + 6]‐cycloadduct (4ab), anti‐exo‐[4 + 2]‐cycloadduct (5ab), and the heterocage (6ab) derived from the intramolecular 1,3‐dipolar cycloaddition reaction of the syn‐endo‐[4 + 2]‐cycloadduct. Analogous endo‐[4 + 6] selectivity in 1,3‐dipolar cycloadditions has not been reported previously. The X‐ray analysis indicates that 6ab has a very long N_sp3–N_sp3 bond distance of 1.617(4) Å. The cycloaddition behaviour is discussed on the basis of transition‐state structures optimized at the B3LYP/6‐31G(d) level of theory, from which predictions of the peri‐, regio‐, and stereoselectivities agreed well with the experimental results. Copyright © 2012 John Wiley & Sons, Ltd.     

Theoretical study on the oxidation of zigzag silicon carbide nanotubes (SiCNTs) by singlet O2

Singlet O₂ produced upon photoexcitation is a very important oxidative reagent. The study on its reaction with nanotube might be useful not only to evaluate the stability of the nanotube upon air exposure and sunlight, but also to modify the properties of the nanotube. Considering the unique properties and wide applications of silicon carbide nanotube (SiCNT), in this paper, we performed extensive density functional theory (DFT) calculations to study the oxidation of a series of zigzag (n,0) SiCNTs (n=6 to 12) by singlet O₂. It is found that the reaction process contains two steps, namely, (i) [2+2] cycloaddition of a singlet O₂ to the Si–C bond, followed by (ii) the dissociation of the O–O bond, leading to the formation of an epoxide configuration with a highly exothermicity (>4.00 eV). Compared with pure SiCNT, the cycloaddition of singlet O₂ on tube leads to the decrease of the band gap, while the formation of the stable epoxy structure render band gap increase. Our results indicate that the SiCNT is more prone to be degraded after exposure to air and sunlight.     

Investigation of the possibility of functionalization of C20 fullerene by benzene via Diels–Alder reaction

C₂₀ fullerene, this novel species with all its pentagonal faces has displayed some unique operations in making fast pericyclic reactions. As an example, the high dienophile character of the C₂₀ fullerene and the ability of this species in making an ultra-fast Diels–Alder reaction with 1,3-butadiene, has been recently reported. Moreover, new experimental reports claim that the C₆₀ fullerene, one of the fullerene family, could make a Diels–Alder reaction with the central ring of anthracene and make the ring non-aromatic. These reports may encourage researchers to do more studies on the properties of this small carbon cage.To address this question, the present research has discussed all the reaction channels of the Diels–Alder cycloaddition of benzene molecule as a 1,3-diene with the C₂₀ fullerene in order to answer this question: “Is C₂₀ fullerene able to make a Diels–Alder reaction with this molecule?”.     

Ultrasound-assisted one-pot three-component synthesis of new isoxazolines bearing sulfonamides and their evaluation against hematological malignancies

In the present study, following a one-pot two-step protocol, we have synthesized novel sulfonamides-isoxazolines hybrids (3a-r) via a highly regioselective 1,3-dipolar cycloaddition. The present methodology capitalized on trichloroisocyanuric acid (TCCA) as a safe and ecological oxidant and chlorinating agent for the in-situ conversion of aldehydes to nitrile oxides in the presence of hydroxylamine hydrochloride, under ultrasound activation. These nitrile oxides could be engaged in 1,3-dipolar cycloaddition reactions with various alkene to afford the targeted sulfonamides-isoxazolines hybrids (3a-r). The latter were assessed for their antineoplastic activity against model leukemia cell lines (Chronic Myeloid Leukemia, K562 and Promyelocytic Leukemia, HL-60).     

Mechanistic study on Mo(CO)6‐catalyzed intramolecular [2 + 2] or [2 + 2 + 1] cycloaddition reaction of 5‐allenyl‐1‐ynes

By means of density functional theory, the Mo(CO)₆‐catalyzed intramolecular [2 + 2] or [2 + 2 + 1] cycloaddition reaction of 5‐allenyl‐1‐ynes was investigated. All the intermediates and transition states were optimized completely at B3LYP/6‐311++G(d,p) level (LANL2DZ(f) for Mo). Calculations indicate that the complexation of 5‐allenyl‐1‐ynes with Mo(CO)₆ occurred preferentially at the triple bond to give the complex M1 and then the complexation with the distal double bond of the allenes generates the complex M5 . In this reaction, Mo(CO)₆‐catalyzed intramolecular [2 + 2] cycloaddition is more favorable than [2 + 2 + 1] cycloaddition. The reaction pathway Mo(CO)₆ + R → M5 → T7 → M12 → M13 → T11 → M18 → P4 is the most favorable one, and the most dominant product predicted theoretically is P4 . The solvation effect is remarkable, and it decreases the reaction energy barriers. Copyright © 2011 John Wiley & Sons, Ltd.     

CX2(X=F, Cl, Br)与CH3CHO中C－C键插入和环加成的理论模拟

采用密度泛函[DFT]和自然键轨道理论[NBO]及高级电子耦合簇[CCSD(T)]和电子密度拓扑分析[AIM]方法, 研究了单重态二卤卡宾CX2(X=F, Cl, Br)与乙醛CH3CHO 中C—C键的插入反应及其环加成的反应机理. 在B3LYP/6-31G(d)水平上优化了各驻点构型, 用频率分析和内禀反应坐标法(IRC)对过渡态进行了验证, 计算了各物种的CCSD(T)/6-31G(d, p)单点能量. 用经Wigner校正的Eyring过渡态理论分别计算了1大气压下主反应通道的热力学与动力学性质, 并对反应通道中构型进行了自然键轨道及电子密度拓扑分析. 结果表明, CF2与CH3CHO反应的主产物是P2F[CH3CF2CHO: 插入CH3CHO中C-C键, 反应I(2)], 而CCl2及CBr2与CH3CHO反应的主产物是P1Cl[Cl2COCHCH3: 成环反应II(1)]及P1Br[Br2COCHCH3: 成环反应III(1)], 1大气压下, 反应I(2)和II(1)及III(1)进行的适宜温度范围分别为400~1300K和400~1000K.     

Theoretical study of the mechanism of cycloaddition reaction between dichloromethylene silylene and formaldehyde

The mechanism of cycloaddition reaction between singlet dichloromethylene silylene and formaldehyde has been investigated using a MP2/6-31G* method, including geometry optimization and vibrational analysis for the stationary points on the potential energy surface. The energies of different conformations are calculated by CCSD(T)//MP2/6-31G* method. From the potential energy profile, it can be predicted that the cycloaddition reaction between singlet dichloromethylene silylene and formaldehyde has three competitive dominant reaction channels: (1) the two reactants first form a highly strained three-membered ring intermediate INT1c, which then isomerizes to an active four-membered ring product P1 via a transition state TS1c by ring-increasing reaction; Subsequently, P1 further reacts with formaldehyde to form the more stable silapolycyclic product P2; (2) the two reactants first form a four-membered ring intermediate INT1b by the [2?+?2] cycloaddition reaction, which then isomerizes to the four-membered ring product P3.1 via a transition state TS3.1, resulting from the chlorine transfer reaction; (3) INT1b further reacts with formaldehyde to form a silapolycyclic intermediate INT4, which then isomerizes to a silapolycyclic product P₄ via a transition state TS4.     

Synergistic effect of dual-frequency ultrasound irradiation in the one-pot synthesis of 3,5-disubstituted isoxazoles

Herein is reported a one-pot three-step process for the regioselective synthesis of 3,5-disubstituted isoxazoles based on copper(I)-catalyzed cycloaddition reaction between in situ generated nitrile oxides (from the corresponding aldehydes) and alkynes, using ultrasound irradiation, avoiding toxic reagents and solvents and isolation/purification of intermediates.The combined use of 40 kHz ultrasonic bath and 20 kHz probe in the presence of copper turnings reduced reaction time to 1 h and resulted in only one final purification step with increased yields, clearly indicating that there is a dual-frequency synergistic effect.In addition, under metal free conditions, the 1,3-dipolar cycloaddition was regioselective giving low to modest yields.     

Ultrasonic-assisted synthesis of chrysin derivatives linked with 1,2,3-triazoles by 1,3-dipolar cycloaddition reaction

The 1,3-dipolar cycloaddition reaction between 7-(3-azidopropoxy)-5-hydroxyflavone and phenylacetylene was carried out to investigate the synthesis of 7-(3-(4-phenyl-1,2,3-triazol-1-yl)propoxy)- 5-hydroxyflavone in presence of ultrasound (sono-synthesis) and absence of ultrasound (conventional method) under relatively optimized solvent and catalyst conditions. The reaction rate was notably accelerated with the help of ultrasound irradiation. An experiment was especially carried out for investigating the acceleration mechanism of ultrasound on the cycloaddition. A novel series of chrysin derivatives linked with 1,2,3-triazoles were obtained by the copper(I)-catalyzed 1,3-dipolar Huisgen cycloaddition reaction using t-BuOH/H(2)O (1:1 v/v) as reaction solvents and CuSO(4)·5H(2)O/sodium ascorbate as the catalyst at room temperature in the presence of ultrasound irradiation. Their structures are elucidated by NMR, ESI MS, IR and Elemental analysis.     

Regioselective 1,3-dipolar cycloaddition of phenanthrolinium N-ylides to substituted arylidene oxazolones

The 1,3-dipolar cycloaddition reactions of phenanthrolinium ylides have been investigated. Thus 15 novel aryl substituted spiro[oxazole-4,10′-pyrrolo[1,2-a][1,10] phenanthrolin]-5-ones were prepared in a regioselective manner, by the treatment of phenanthrolinium ylides with (Z)-arylidene oxazolones.     

Intramolecular Diels–Alder reaction in enyne–allenes: a computational investigation and comparison with the Myers–Saito and Schmittel reactions

The reaction mechanisms as well as substituted effect and solvent effect of the enyne–allenes are investigated by Density Functional Theory (DFT) method and compared with the Myers–Saito and Schmittel reactions. The Myers–Saito reaction of non‐substituted enyne–allenes is kinetically and thermodynamically favored as compared to the Schmittel reaction; while the concerted [4 + 2] cycloaddition is only 1.32 kcal/mol higher than the C₂? C₇ cyclization and more exothermic (Δ_RE = ?69.38 kcal/mol). For R₁ = CH₃ and t‐Bu, the increasing barrier of the C₂? C₇ cyclization is higher than that for the C₂? C₆ cyclization because of the steric effect, so the increased barrier of the [4 + 2] cycloaddition is affected by such substituted electron‐releasing group. Moreover, the strong steric effect of R₁ = t‐Bu would shift the C₂? C₇ cyclization to the [4 + 2] cycloaddition. On the other hand, for R₁ = Ph, NH₂, O^?, NO₂, and CN substituents, the barrier of the C₂? C₆ cyclization would be more diminished than the C₂? C₇ cyclization due to strong mesomeric effect; the reaction path of C₂? C₇ cyclization would also shift to the [4 + 2] cycloaddition. The solvation does not lead to significant changes in the potential‐energy surface of the reaction except for the more polar surrounding solvent such as dimethyl sulfoxide (DMSO), or water. Copyright © 2009 John Wiley & Sons, Ltd.     

Recent advances in 1,3-dipolar cycloaddition reactions on solid supports

Solid-phase methods are of a great significance in organic synthesis. Recent developments of these methods are providing new ways to construct libraries of small organic molecules. Five-membered heterocyclic compounds, which can be utilized in a variety of applications, are formed in the 1,3-dipolar cycloaddition reaction between dipolarophiles and dipoles. This review deals with the solid-phase synthesis of heterocycles via [3+2] cycloaddition reaction. Cycloaddition reactions of polymer-bound dipoles and polymer-bound dipolarophiles and intramolecular solid-phase cycloadditions are discussed in separate sections. Reactions of dipolarophiles such as alkenes, alkynes, and imines with dipoles such as azomethine ylides, azomethine imines, nitrile imines, azides, nitrones, and nitrile oxides are described. The recent literature up to December 2003 is covered.     

Chemistry of a novel zerovalent ruthenium π-acidic alkene complex,Ru (η6-1,3,5-cyclooctatriene)(η2-dimethyl fumarate)2

A novel zerovalent ruthenium complex with a π-acidic ligand, Ru(η⁶-cyclooctatriene)(η²-dimethyl fumarate)₂ (1), was prepared from Ru(η⁴-cyclooctadiene)(η⁶-cyclooctatriene) [Ru(cod)(cot)]. Complex 1 or Ru(cod)(cot) catalyzes various new carbon-carbon bond-forming reactions that include the [2 + 2] cycloaddition of alkenes and alkynes via ruthenacycles, the creation of a new hydrocarbon, pentacyclo[6.6.0.0^2,6.0^3,13.0^10,14]tetradeca-4,11-diene [PCTD], by dimerization of 2,5-norbornadiene via C-C bond cleavage, and the codimerization of alkynes and/or alkenes. Complex 1 was shown to be an excellent mother complex for various zerovalent ruthenium complexes. Complex 1 reacts with amines, phosphines or water to give new zerovalent ruthenium complexes with the ligands. The resulting aqua complexes have a water ligand with an oxygen atom that is a chiral center, i.e., ruthenium complexes with a ‘chiral water’ ligand were prepared and fully characterized.     

Unexpected regio- and stereoselective [4 + 3] cycloaddition reaction of azomethine ylides with benzylidene thiazolidinediones: synthesis of pharmacologically active spiroindoline oxazepine derivatives and theoretical study

Molecular Diversity - An unexpected regio- and stereoselective [4?+?3] cycloaddition reaction of azomethine ylides with 5-benzylidenethiazolidine-2,4-diones has been successfully...     

Cycloaddition of CS2 to N‐benzylaziridine to synthesize N‐benzylthiazolidine‐2‐thione: a novel reaction route proposed by DFT Study

N‐Benzylthiazolidine‐2‐thione is the key intermediate for the synthesis of pharmaceutically important compounds. A novel route for the synthesis of N‐benzylthiazolidine‐2‐thione through cycloaddition of CS₂ with N‐benzylaziridine in the presence of 1,3‐di‐tert‐butylimidazolium‐2‐dithocarboxylate ( catalyst I ) has been proposed by reliable computations performed within the formalism of density functional theory. The mechanism of the proposed reaction is similar to the cycloaddition of tertiary aziridines and carbon dioxide using a recyclable catalyst that is reported to provide access to 3‐substituted 2‐oxazolidones with excellent yield. Because the rate determining step needs to surmount a high energy barrier, the reaction route has been deciphered in high boiling solvent (1, 2‐ethanediol). The highlight of the mechanistic route detailed here is that the proposed pathway is a cyclic process that is exothermic in nature with the regeneration of the catalyst and involves simple reagents. Copyright © 2016 John Wiley & Sons, Ltd.     

Facile and highly diastereo and regioselective synthesis of novel octahydroacridine-isoxazole and octahydroacridine-1,2,3-triazole molecular hybrids from citronella essential oil

A novel and highly efficient synthetic approach for the expedite construction of new octahydroacridine-isoxazole- and octahydroacridine-1,2,3-triazole-based molecular hybrids is first reported. Rapid access to the octahydroacridine core was achieved in a highly diastereoselective fashion via cationic Povarov reaction of N-propargyl anilines and citronella essential oil (Cymbopogon nardus). The subsequent 1,3-dipolar and Cu (I) catalyzed alkyne-azide cycloaddition reaction of the terminal alkyne fragment with the corresponding oxime or azide affords the desired 3,5-isoxazoles and 1,2,3-triazoles, respectively, as interesting molecular hybrid models for pharmacological studies.

     

High diastereoselectivity induced by intermolecular hydrogen bonding in [3 + 2] cycloaddition reaction: experimental and computational mechanistic approaches

A diastereoselective [3 + 2] cycloaddition of N‐aryl substituted maleimides with N,α‐diphenyl nitrone possessing 11‐hydroxyundecyloxy as a flexible substituent was performed. Experimental and comprehensive mechanistic density functional theory studies reveals that intermolecular H‐bonding and steric repulsive interaction predominate exo‐Z and exo‐E cycloaddition transition states, respectively. The reaction proceeded smoothly depending on the reactants and gave a good yield of (syn) cis‐isoxazolidine or (anti) trans‐isoxazolidine as a single diastereomer.     

Intramolecular 1,3-dipolar cycloaddition reactions in the synthesis of complex annelated quinolines, α-carbolines and coumarins

In this study, we report the synthesis of several novel dihydroisoxazole-, tetrahydroisoxazole- and dihydropyrazole-fused pyrido[2,3-b]quinolines, α-carbolines, and pyrido[2,3-c]coumarins, respectively, from simple precursors and by exploring intramolecular 1,3-dipolar cycloaddition reactions involving nitrile oxides, nitrones, and nitrile imines as 1,3-dipoles.