Sustainable production of high-energy-density jet fuel via cycloaddition reactions

Developing an energy supply-chain based on renewable biomass holds great potential to build a low carbon society.High-energy-density(HED)jet fuel,featuring unique fused/strained cycloalkanes,is of great significance for volume-limited military aircrafts,as their high density and combustion heat can extend flight duration and increase the payload.Therefore,the exploration of biomass-based routes towards HED fuel has drawn much attention over the past decade.Cycloaddition reaction features rapid construction of various carbocycles in an atom-and step-economical fashion.This elegant strategy has been widely applied in the manufacture of sustainable HED fuel.Here we carefully summarize the progress achieved in this fascinating area and the review is categorized by the cycloaddition patterns including[4+2],[2+2],[4+4],and[2+1]cycloadditions.Besides,the energy densities of the as-prepared biofuels and petroleumbased fuels(conventional Jet-A and advanced JP-10)are also compared.This review will provide important insights into rational design of new HED fuel with different ring-types/sizes and inspire the chemists to turn those literature studies into practical applications in military field.

Rhodium Catalyzed [2π + 2π + 2π]-Cycloaddition of Alkynyl-Ynamides and Carbon Disulfide to Indolo-Thiopyrane Thiones

The synthesis of new indoloannulated thiopyranethiones is reported. The key-step is a rhodium-catalyzed [2 + 2 + 2]-cycloaddition of alkynyl-ynamides with carbon disulfide to close the pyrrole and the thiopyranethione rings simultaneously. A violet idolothiopyrane thione or a mixture of the violet and a red isomer result from [RhCl(C8H14)2]2/3BINAP catalyzed cycloadditions, the regiochemistry is controlled by the substitution pattern on the alkynyl-ynamide.

Theoretical Study on Mechanism of Cycloadditional Reaction Between Dichloro-Germylidene and Formaldehyde

Mechanism of the cycloadditional formaldehyde has been investigated reaction between singlet with MP2/6-31G^＊ method, dichloro-germylidene and including geometry optimization, vibrational analysis and energies for the involved stationary points on the potential energy surface. From the potential energy profile, we predict that the cyeloaddition reaction between singlet dichloro-germylidene and formaldehyde has two competitive dominant reaction pathways, going with the formation of two side products （INT3 and INT4）, simultaneously. Both of the two competitive reactions consist of two steps, two reactants firstly form a three-membered ring intermediate INT1 and a twisted four-membered ring intermediate INT2, respectively, both of which are barrier-free exothermic reactions of 41.5 and 72.3 kJ/mol; then INT1 isomerizes to a four-membered ring product P1 via transition state TS1, and INT2 isomerizes to a chlorine-traasfer product P2 via transition state TS2, with the barriers of 2.9 and 0.3 kJ/mol, respectively. Simultaneously, P1 and INT2 further react with formaldehyde to form INT3 and INT4, respectively, which are also barrier-free exothermic reaction of 74.9 and 88.1 kJ/mol.

Enantioselective synthesis of chiral phosphonylated 2,3-dihydrofurans by copper catalyzed asymmetric formal [3+2] cycloaddition of propargylic esters with β-keto phosphonates

Copper catalyzed asymmetric formal [3＋2] cycloaddition of propargylic esters toβ‐keto phospho‐nates for the synthesis of chiral phosphonylated 2,3‐dihydrofurans was developed. By using a bulky and structurally rigid tridentate ketimine P,N,N ligand, a series of optically active phosphonylated 2,3‐dihydrofurans were prepared in high yield and up to 92%ee.

Facile preparation of bi-functional iron doped mesoporous materials and their application in the cycloaddition of CO2

Two kinds of bi-functional transition metal doped mesoporous materials(Fe-HMS and Fe-MCM-41) are prepared using one-step hydrothermal method and then treated with hydrochloric acid ethanol solution.The N2 adsorption and HRTEM results show that both of Fe-HMS and Fe-MCM-41 possess mesoporous structure. The UV–vis results suggest that the Fe species are mainly located within the framework. The basicity of as-prepared samples was studied by temperature programmed desorption using CO2 as probe molecule(CO2-TPD). The catalytic performance of Fe-HMS and Fe-MCM-41 in CO2 cycloaddition largely depends on the amount of the accessible basic sites. The acid–base active sites, framework Fe and PDDA species cooperatively catalyze the CO2 cycloaddition for the production of cyclic carbonates under the condition without any co-catalyst. The conversion of epichlorohydrin(ECH) is 97.4% and the selectivity of chloropropene carbonate is 92.9% under optimal conditions. The approximate rate constant of cycloaddition reaction of CO2 with ECH under optimum reaction temperature is calculated. It is worth noting that the Fe-HMS material shows superior reusability than Fe-MCM-41. In addition, this work provides a facile way on the synthesis of bi-functional acid–base heterogeneous catalyst with outstanding catalytic performance for the fixation of CO2.

Salen-Cu(Ⅱ)@MIL-101(Cr)as an efficient heterogeneous catalyst for cycloaddition of CO2 to epoxides under mild conditions

A double active center system, namely Salen-Cu（Ⅱ）@MIL-101（Cr）, was successfully synthesized via the"ship in a bottle" approach, which acted as a bifunctional material for both capture and conversion of COin a single process. For the first time, Salen-Cu（Ⅱ）@MIL-101（Cr） catalyst was developed for the synthesis of propylene carbonate from COand propylene oxide under room temperature and ambient pressure with a yield of 87.8% over 60 h. Furthermore, the reaction mechanism was also discussed.

Studies on New Additions to 5-Methoxy-2 (5H)-Furanone: 1, 4-Addition of Grignard Reagents, and 1,3-Dipolar Cycloaddition of Silyl Nitronates

1,4-Addition reaction of Grignard's reagent to 5-methoxy-2(5H)-furanone 1 was accomplished. which provided a new possible route for synthesizing beta -alkyl-Y-alkyloxy-Y-butyrolactone. A novel concise method of preparing fused heterocyclic compounds was offered by 1,3-dipolar cycloaddition reaction of silyl nitronates to 1.

A Facile Synthesis of Indolizines by 1，3－Dipolar Cycloaddition of Pyridinium and Related Heteroaromatic Ylides with Alkenes in the Presence of TPCD，Py_4Co（HCrO_4）_2

facile one-step method is presented for the synthesis of indolizines in moder-ate to high yields by reaction of pyridinium, quinolinium and isoquinolinium ylideswith acrylonitrile, methyl acrylate and diethyl maleate respectively in the presenceof tetrakis-pyridino-cobalt(Ⅱ)dichromate (TPCD) in DMF.

Synthesis of Novel Discotic C_(60)-triphenylene Derivative by 1,3-Dipolar Cycloaddition

1 Introduction Fullerene has received considerable attention and a great researching interest due to its unique structure and interesting properties[1―3]. Many functional groups have been introduced, often region- or stereo-selectively, for tuning the physical properties of C60and for constructing supramoleculararchitectures^[4-6].

SYNTHESIS AND CHARACTERIZATION OF TRIAZOLE CONTAINING LIQUID CRYSTALLINE POLYMERS THROUGH 1,3-DIPOLAR CYCLOADDITION POLYMERIZATION

Liquid crystalline polymers containing 1,2,3-triazole units as linking groups have been synthesized from the monomers containing triad ester diazide and flexible dialkyne ester by 1,3-cycloaddition reaction and were characterized. Click reaction of azide and alkyne functionals catalyzed by Cu(I) yielded target polyesters with 1,2,3-triazole groups.The structure of the polymer was confirmed by spectral techniques.GPC analysis reveals that the polymers have moderate molecular weight with narrow distribution.H...

Ionization of a covalent organic framework for catalyzing the cycloaddition reaction between epoxides and carbon dioxide

Covalent organic frameworks(COFs),with two dimensional(2D-)or three dimensional(3D-)structures,have accessible open channels or nanopores,with uniform sizes ranging from angstroms to nanometers and have emerged as an excellent and promising platform for designing catalysts or catalyst carriers.Herein,a 2 D-COF grafted with a 1-alkyl-3-methylimidazolium-based ionic liquid(AMIMBr@H2 P-DHPh COF)on the channel walls was synthesized and utilized as a highly efficient heterogeneous catalyst for the chemical fixation of CO2 via a reaction with epoxides under solvent-free and co-catalyst-free conditions.The as-synthesized AMIMBr@H2 P-DHPh COF shows excellent catalytic activity in promoting the cycloaddition reactions between epoxide and CO2;the excellent catalytic activity was maintained for up to five cycles.Advantages like high porosity,functional versatility,easy modification of COFs,and high catalytic activity of ionic liquids,have been realized in a single material.

Highly active binuclear Cu(Ⅱ) catalyst bearing an unsymmetrical bipyridine-pyrazole-amine ligand for the azide-alkyne cycloaddition reaction

Ligands containing NH groups often show special characteristics.In this paper,a well-defined dinuclear Cu（II） complex bearing an unsymmetrical bipyridine-pyrazole-amine ligand was synthesized by the condensation of N–H to release H2O.Using sodium L-ascorbate as a reductant,the binuclear complex showed excellent activity in 1,3-dipolar cycloaddition reactions between alkynes and azides to obtain 1,4-disubstituted triazoles in 95%–99% isolated yields.

NEW HETEROCYCLIC SYSTEM SYNTHESIS VI． THE CYCLOADDITION DERIVATIVES OF 1，5－BENZOTHIAZEPINE AND 1，5－BENZODIAZEPINE

Dihydro-1H-1, 5-benzodiazepines and 1-benzoy1-2, 3-dihydro-1H-1H-1,5-benzodiazepines react with .α-carbonylkelenes, generated from 2-diazo-1,3-diphenyl-1,3-propandione or 2-diazo-1-phenyl-1,3-butandione by heating, to give 4a,5, 6, 12-letralydro- 1H,7H-1,3-oxazino[3,2-d][1,5]-benzodiazepine-1-ones,a new ring system. 2, 3-Dihydro-1H-1,5-benzodiazepines also afford,dducts of H-N bond,with a carbonylketenes, 2-aryt-1-(2-benzoyl-phenylacelyl)-4-phenyl-2,3-dihydro-1H-1,5-benzodiazepines. Addition of henzonitrile N-phenylimine,yielde in situ from the N-phenyl benzenecarbohydrazic chloride,to 2, 4-diaryl-2, 3-dihydro-1,5-benzothiazepines and 1H-1,5-benzodiazepine gave 3a, 5-diaryl-1, 3-diphenyl-3a, 4, 5, 11 tetralydro-3H-1, 2, 4-triazolo [4, 3-d][1. 5]benzothiazepine and 3H,6H-1, 2, 4 triazolo[4, 3-d][1, 5] benzodiazpine, respectively.

Chiral basket-handle porphyrin-Co complexes for the catalyzed asymmetric cycloaddition of CO_2 to epoxides

The catalytic synthesis of cyclic carbonates via the cycloaddition of CO2 to epoxides is a standard methodology for CO2 fixation.For this purpose,chiral basket-handle porphyrin-Co complexes were devised,prepared,and fully characterized by nuclear magnetic resonance,mass spectrometry,Fourier transform infrared spectroscopy,ultraviolet-visible spectroscopy,and specific rotation.The proposed metalloporphyrin catalysts were synthesized with either 1,1'-bi-2-naphthol or L-phenylalanine,which have different chirality,and then applied to the coupling of propylene oxide and CO2 for generating chiral cyclic carbonates with good enantioselectivity under extremely mild conditions in the presence of tetrabutyl ammonium chloride as a co-catalyst.The good enantioselectivity in the cycloaddition reaction is attributed to a synergistic interplay between the chiral porphyrin catalysts and the substrate.The mechanism and enantioselectivity of the asymmetric cycloaddition reaction is discussed.

Mechanistic Investigation on Rhodium(III)-Catalyzed Cycloaddition of 2-Vinylphenol Derivatives with Ethyne or Carbon Monoxide by DFT Study

Rhodium-catalyzed cycloaddition reaction was calculated by density functional theory M06-2X method to directly synthesize benzoxepine and coumarin derivatives.In this work,we conducted a computational study of two competitive mechanisms in which the carbon atom of acetylene or carbon monoxide attacked and inserted from two different directions of the six-membered ring reactant to clarify the principle characteristics of this transformation.The calculation results reveal that:(i)the insertion process of alkyne or carbon monoxide is the key step of the reaction;(ii)for the(5+2)cycloaddition reaction of acetylene,higher energy is required to break the Rh−O bond of the reactant,and the reaction tends to complete the insertion from the side of the Rh−C bond;(iii)for the(5+1)cycloaddition of carbon monoxide,both reaction paths have lower activation free energy,and the two will generate a competition mechanism.

Kinetics and mechanistic investigation of epoxide/CO2 cycloaddition by a synergistic catalytic effect of pyrrolidinopyridinium iodide and zinc halides

Formation of styrene carbonate (SC) by the cycloaddition of CO2 to styrene oxide (SO) catalysed by pyrrolidinopyridinium iodide (PPI) in combination with zinc halides (ZnCl2, ZnBr2 and ZnI2) was investigated. Complete conversion of the SO to SC was achieved in 3 h with 100% selectivity using 1/0.5 molar (PPI/ZnI2) catalyst ratio under mild reaction conditions i.e., 100℃ and 10 bar CO2 pressure. The synergistic effect of ZnI2 and PPI resulted in more than 7-fold increase in reaction rate than using PPI alone. The cycloaddition reaction demonstrated the first-order dependence with respect to the epoxide, CO2 and catalyst concentrations. Moreover, the kinetic and thermodynamic activation parameters of SC formation were determined using the Arrhenius and Eyring equations. The positive values of △H(42.8 kJ mol^-1) and △G(102.3 kJ mol^-1) revealed endergonic and chemically controlled nature of the reaction, whereas the large negative values of △S(-159.4 J mol^-1 K^-1) indicate a highly ordered activated complex at the transition state. The activation energy for SC formation catalyzed by PPI alone was found to be 73.2 kJ mol^-1 over a temperature range of 100-140℃, which was reduced to 46.1 kJ mol^-1 when using PPI in combination with ZnI2 as a binary catalyst. Based on the kinetic study, a synergistic acid-based reaction mechanism was proposed.

Study on Unexpected Cycloaddition Reactions of Imines with THF

An unexpected tricyclic compound 2,3,3a,4,5,9b-hexahydrophenylfuro[3.2-c] quinoline 4 and its aromatized product 6 were obtained when the cycloaddtion of imine 1 and substituted norbornene 2 was carried out in THF with a catalytic amount of boron trifluoride. The structures of the products were determined by spectral data and the mechanism of reaction was substantiated by the imitation reaction.

Studies on Different Cycloaddition Reactions Catalyzed by ZnCl_2

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1,3-Dipolar Cycloaddition Reaction between Vinyl Acetate and N-Alkyl Hydroxypyridinium Halide

1, 3 Dipolar cycloaddition reaction between vinyl acetate and 3-hydroxypyridiniun betaine was performed under solid-liquid phase transfer catalytic condition, This reaction has been successfully used on the synthesis of an analogue of Bao-Gong-Teng A.

1,3-Dipolar Cycloaddition of Substituted Benzonitrile Oxide to 5-(R)-(l-Menthyloxy)-2(5H)-furanone

Several isoxazoline compounds were obtained by the 1,3-dipolar cycloaddition of benzonitrile oxide to 5-(R)-(l-menthyloxy)-2(5H)-furanone. The reaction condition was investigated preliminarily, the structures of these compounds have been established via the analysis of NMR data(involved NOEID or HMBC) and the reaction seems occurred regioselectively.