Bond Migration Research Articles

Insights into the pore size distribution of amorphous silica membranes using gas permeation activation energies

Silica-based membranes exhibit significant promise for the separation of hydrogen from other larger gas molecules based on size sieving mechanism, particularly when employed in membrane reactors. Nevertheless, the migration of silanol bonds (Si–OH) formed under hydrothermal conditions leads to alterations in pore size, ultimately compromising the performance of the membrane. Therefore, this study focuses on determining the pore size of cobalt-doped silica membranes before and after hydrothermal treatment by the apparent activation energy of gas permeation. The Oscillator model and the effective medium theory are employed to estimate the potential pore size distribution, as well as to calculate the apparent activation energy and permeability. The calculated apparent activation energy is compared with experimental data to identify the most probable pore size distribution, which showed the minimum activation energy error to the experimental value. The calculated permeability based on the identified pore size distribution is in line with experimental permeability, which validated the identified pore size distribution. Since silica-based membrane is generally applied in hydrothermal conditions, our model successfully identifies the changes in pore size of silica-based membranes after hydrothermal treatment. The results demonstrated that hydrothermal treatment significantly impacts the pore size of silica-based membranes. Specifically, 5-membered rings are prevalent in the intact membrane, but after hydrothermal treatment, there is a gradual shift of the pore size distribution towards larger pores, potentially leading to a decrease in sieving performance. This methodology presents a promising approach for determining intriguing pore size information of porous materials.

Ultrasound-assisted synthesis of novel undecylenic estolides: Modeling and Tribological characterization

Abstract To overcome the issues related to low-temperature characteristics and thermal degradation of fatty acid based lubricant base stocks, chemical modification is essential. To mitigate these shortcomings, considering unsaturated undecylenic acid, the formation of estolides is one of the best transformations considering application in lubricants. Ultrasonic-assisted sulfuric acid-catalyzed synthesis of estolides of undecylenic was modeled using response surface methodology (RSM) and subsequently validated using artificial neural network (ANN) for known and unknown input variables. At optimal reaction conditions of reaction temperature of 56°C, catalyst loading of 0.63 mole-equivalent, and reaction time of 1.61 hours, estolides with estolide number (EN) of 2.58, extraordinary low pour point (PP) of −52°C and better resistance to thermal degradation was obtained. The thermal degradation was evaluated using thermogravimetric analysis (TGA) to find improved resistance toward degradation due to the formation of estolides. Further, tribological properties like wear characteristics, load carrying capacity, and oxidative stability were studied for 5% blends in SN 70 base oil. The anti-wear ability of the estolides was found to be superior to undecylenic acid, with a lower coefficient of friction, scar diameter, depth, and volume. The blend containing estolide was found to have load carrying capacity as high as 800 kgf. Moreover, owing to the double bond migration during the reaction, the oxidative stability of estolides was found to be inferior to the terminally unsaturated undecylenic acid.

Palladium-Catalyzed Three-Component Cascade Carbonylation Reaction to Construct Benzofuran Derivatives.

A novel three-component cyclization carbonylation reaction of iodoarene-tethered propargyl ethers with amine and CO is reported. This palladium-catalyzed cascade reaction undergoes a sequence of oxidative addition, unsaturated bond migration, carbonyl insertion, and nucleophilic attack to deliver the benzofuran skeleton. Both aromatic amines and aliphatic amines could proceed smoothly in this transformation under one atm of CO.

Stepwise Carbene Transfer Reaction with Alkenes beyond Cyclopropanation

AbstractMetal carbene transfer reactions have been well-established as an indispensable tool in modern organic synthesis, especially in the construction of C–C and C–X bonds with high efficiency and selectivity. Among these, stepwise carbene transfer reaction with alkenes beyond classical cyclopropanation reaction has been demonstrated as a practical method for the effective olefinic C–H/C–C bond functionalization. This review highlights the recent achievements in this area for the direct C–C bond formation involving metal carbene species with alkenes through a through stepwise reaction pathway. The content of this review is organized into three general categories according to the types of the reactions, including (i) direct nucleophilic addition of alkenes with metal carbene species, (ii) cross-coupling reaction via an alkenylic C–H bond activation and migration insertion sequence, and (iii) catalytic coupling reaction involving radical intermediate. Considering this rapidly evolving field, detailed reaction mechanism, current limitations, and future research directions are discussed.1 Introduction2 Nucleophilic Addition of Alkenes to Metal Carbene Species2.1 Using Polarized Alkenes2.2 Using Unactivated Alkenes2.3 Cascade Reactions3 Cross-Coupling Reaction Involving Metal Carbene Migratory Insertion Process4 Coupling Reaction Involving Radical Intermediate5 Conclusions and Perspectives

Synergy between Lewis acidic metal sites and silanols in Sn- and Ti-Beta for conversion of butenes by DRIFTS

The synergistic effect of Lewis acidic Sn/Ti sites and silanols in Sn- and Ti-Beta zeolites on the reaction pathways and mechanisms of the conversion of butenes was investigated by in situ diffuse reflectance infrared Fourier transform spectroscopy. The double bond migration reaction of n-butene to cis-2-butene followed an AB–AD mechanism, in which hydrogen abstraction (AB) from the methylene group at Lewis acidic Sn/Ti sites afforded an allyl intermediate, followed by synergistic hydrogen addition (AD) on silanols. In contrast, the following cis–trans isomerization reaction between cis-2-butene and trans-2-butene, and the activation of isobutene, followed an AD–AB mechanism via hydrogen addition to the double bond of butenes on silanols, forming an alkoxyl group rather than allyl group as the intermediate owing to the absence of a methylene group in 2-butene and isobutene.

Ferrocenyl carborane conjugates with allyl functionalities: Synthesis and properties

A series of novel hybride ferrocene carborane derivatives containing allyl functionalities at the carborane carbon atoms were firstly synthesized in a good yield providing their potential applications in various fields of material science. Synthesized compounds were characterized using various spectroscopic techniques like IR, ESI-MS, 1H and 11B NMR data. Some compounds were investigated by cyclic voltammetry. The total charge density around each atom was calculated for 1-allyl-9-ferrocenylmethyl-m-carborane. Particular attention has been focused on the analysis of 1H NMR spectra of diallyl-substituted ferrocene carboranes which made it possible to discover the migration of the double bond in allyl substituent and the formation along with diallyl derivative of the corresponding allylpropenyl isomer compounds.

Total Syntheses of Hosieines A-C.

The collective total syntheses of (±)-hosieines A-C with a cage-like tetracyclic framework have been realized,which includes the first syntheses of hosieines B-C. The key strategy of the synthesis employs a one-pot domino reaction that involves Cu-catalyzed [3+2] cycloaddition, 1,6-enone formation, and 1,6-aza-Michael addition forming the 5/6/6-aza-tricyclic skeleton. Other salient synthetic tactics comprise a challenging double bond migration and a 1,4-aza-Michael addition reaction to afford the tetracyclic framework.

Gas chromatography-mass spectrometry selected ion monitoring and gas chromatography-tandem mass spectrometry selected reaction monitoring analyses of mono-, di- and tri-unsaturated C25 highly branched isoprenoid alkene biomarkers in sea ice and sediment samples: A comparative study.

The efficiency of selected ion monitoring (SIM) and selected reaction monitoring (SRM) analyses for the quantification of three mono-, di- and tri-unsaturated highly branched isoprenoid (HBI) alkenes (IP25 , IPSO25 and HBI III, respectively), often used as proxies for the occurrence of Arctic and Antarctic sea ice or the adjacent open waters, was compared. Gas chromatography (GC)-mass spectrometry (MS)/SIM and GC/MS/MS/SRM analyses were carried out on dilute solutions made from purified standards of these three HBIs, and then on hydrocarbon fractions of several sediment and sea ice sample extracts. More efficient and specific SRM transitions were selected after collision-induced dissociation of each precursor ion at different collision energies. SRM analysis avoided any overestimation of IP25 resulting from the contribution of the coeluting 13 C mass isotopomer of IPSO25 (M+ ˙ + 2) to the SIM target ion. In contrast, SRM analysis is less reliable for IPSO25 quantification in cases where several regio-isomers are present, likely due to intense double bond migrations following electron impact. In the case of HBI III, SRM analysis constitutes a potentially suitable alternative to SIM analysis, especially in terms of improving limit of detection. Despite the intense migrations of HBI double bonds under electron ionization, the selected SRM transitions should be more suitable than SIM target ions for IP25 and HBI III quantification in complex hydrocarbon fractions of natural samples. However, the advantage is less evident for IPSO25 due to the presence of numerous regio-isomers.

Equivalent Response Strategy for Sensing Total Biothiols in Human Serums and Living Cells Using a Hemicyanine-Based Self-Immolative Probe.

Biothiols including cysteine (Cys), homocysteine (Hcy), and glutathione (GSH) are crucial in maintaining the redox balance in the body, and the metabolism and transportation of biothiols rely on the coreaction of diverse proteins and enzymes. The abnormal concentrations and metabolism of biothiols are closely associated with many diseases. However, due to the same active reaction site of the sulfydryl group in biothiols, it is inevitable to bear a confused signal of mutual influence on both nonselective detection and discriminate detection, which presents a serious challenge of accurately sensing or imaging the three biothiols. By assigning an α,β-unsaturated ketone moiety as a Michael acceptor to trigger thiols to complete the irreversible equivalent domino response processes of nucleophilic addition, olefinic bond migration, and self-immolation, a targeted strategy was rationally pointed out, and herein, a hemicyanine-based probe CyOCy was prepared as a proof of strategy demonstration. The new probe could be equivalently lit up by Cys, Hcy, GSH, and even biothiol combinations (Cys/Hcy, Cys/GSH, Hcy/GSH, or Cys/Hcy/GSH) with unified linear ranges, detection limits, and response times. The probe CyOCy has been successfully used for the accurate quantification of total biothiols in the serum samples of healthy persons and coronary heart disease patients. In addition, the probe has been applied for cell screening, exogenous biothiol imaging, and monitoring drug-induced biothiol fluctuations. The purposive thinking of this work may provide an effective avenue for the accurate sensing of multicomponent samples.

Iron(iv) alkyl complexes: electronic structure contributions to Fe–C bond homolysis and migration reactions that form N–C bonds from N2

Silylation of iron-alkyl-dinitrogen complexes gives high-spin iron(iv) products that also have an iron(ii) resonance structure. The stability and reactivity of these compounds depends on the alkyl group, with insertion and homolysis observed.

Hydroxyl-Directed Regio- and Diastereoselective Allylic Sulfone Reductions with [Sm(H2O)n]I2.

Allylic 1,2- and 1,3-hydroxy phenyl sulfones undergo regioselective and diastereoselective desulfonylation with double bond migration upon treatment with [Sm(H2O)n]I2. Selectivity in these reactions is thought to arise from the formation of a chelated organosamarium intermediate followed by intramolecular protonation by samarium-bound water, which is supported by observed diastereoselectivity and stereospecificity trends along with deuterium labeling experiments. The reaction was then featured in the synthesis of the phenolic fragment of the thailandamide natural products.

The chemistry of Anderson’s test for codeine

The Anderson test for codeine entails the interaction of codeine with concentrated nitric acid and heating to dryness. These drastic conditions give rise to a long series of reactions that is provided for the first time. The initial steps are salt formation, codeine nitrate, followed by nitration of the aromatic ring at the activated position, C-2. Then occurs a molecular rearrangement analogue to the transformation of morphine to apomorphine. This implies a series of reactions that include dehydration of the allylic alcohol, double bond migration, 1,3-chain migration, cyclohexadiene formation, ring opening of the dihydro-furane ring followed by formation of a dihydro-phenanthrene structure. The last stage involves methylamine evolution after two C─N fissions and alkalinization of the reaction medium in order to obtain the free amine.

Synthesis of Berkeleylactone A by Ring‐Closing Alkyne Metathesis

AbstractA new route to the macrolactone antibiotic berkeleylactone A was developed. As a key step, a ring‐closing alkyne metathesis (RCAM) of an ester substrate featuring 1‐propynyl termini was used. The carboxylic part of the substrate was easily assembled using alkyne chemistry, like carboxylation of a diyne followed by isomerization of the ynoate section to a dienoate and dihydroxylation of the 4,5‐double bond. The synthesis of the alcohol part of the ester started with opening of (R)‐propylene oxide with an acetylide and was followed by two triple bond migrations. After successful RCAM which formed the C8−C9 bond, the triple bond was selectively hydrogenated to the corresponding alkene before the 4,5‐diol was oxidized to the 5‐hydroxy‐4‐oxo derivative. At this stage, the thioether was formed and the 8,9‐double bond reduced. We also prepared the 8,9‐didehydro analog of berkeleylactone A. However, it turned out that its antimicrobial activity was slightly reduced.

Phosphine-Catalyzed [3+2] Annulation of Hepta-2,3,5-trienedioates with Alkenes for the Construction of Exocyclic Olefinic Cyclopentenes.

Hepta-2,3,5-trienedioates 1 have been employed as substrates to explore Lewis base-catalyzed annulation reactions. This leads to the discovery of a phosphine-catalyzed [3+2] annulation of 1 with electron-deficient alkenes for the construction of exocyclic olefinic cyclopentenes in good yields and moderate E:Z ratios under mild conditions. The annulation is believed to proceed in a tandem [3+2] cyclization and double bond migration in which the ε-ester is crucial to both processes. This reaction also showcases a substrate-controlled divergent reactivity compared to that of a previous report.

Dual-Hydrogen-Bond Donor and Brønsted Acid Cocatalysis Enables Highly Enantioselective Protio-Semipinacol Rearrangement Reactions.

A catalytic protio-semipinacol ring-expansion reaction has been developed for the highly enantioselective conversion of tertiary vinylic cyclopropyl alcohols into cyclobutanone products bearing α-quaternary stereogenic centers. The method relies on the cocatalytic effect of a chiral dual-hydrogen-bond donor (HBD) with hydrogen chloride. Experimental evidence is provided for a stepwise mechanism where protonation of the alkene generates a short-lived, high-energy carbocation, which is followed by C-C bond migration to deliver the enantioenriched product. This research applies strong acid/chiral HBD cocatalysis to weakly basic olefinic substrates and lays the foundation for further investigations of enantioselective reactions involving high-energy cationic intermediates.

Anti-inflammatory lanostane triterpenoids with rearranged spirobi[indene] scaffold and their biogenetically related analogues from Euphorbia maculata

Phytochemical investigations on the ethanol extract of the whole plant of Euphorbia maculata Linn. Resulted in the identification of 16 lanostane-related triterpenoids, including 11 undescribed ones, namely spiromaculatols A–C (1–3) and euphomaculatoids A–H (4–11). The structural determinations of the previously undescribed ones (1–11) were elucidated based on the interpretation of comprehensive spectroscopic data, quantum chemical calculation, as well as X-ray crystallographic experiments. Spiromaculatols A–C (1–3) possess a rare spirobi [indane] skeleton, which was biosynthetically derived from the 7 (8 → 9)-abeo bond migration of lanostane precursors. The biological activity of compounds 1–3, 5, 7, and 12–13 displayed inhibitory effect on the release of NO in an LPS-activated RAW264.7 cells model. Molecular mechanism study indicated that the most potent spiromaculatol C (3) can reduce the nuclear translocation of NF-κB p65 and decrease the transcriptional expressions of its downstream pro-inflammatory mediators.

Nitrile Oxide, Alkenes, Dipolar Cycloaddition, Isomerization and Metathesis Involved in the Syntheses of 2-Isoxazolines.

The involvement of 1,3-dipolar cycloaddition (1,3-DP), double bond migration, metathesis, and nitrile oxide (including in situ-generated nitrile oxide) as dipoles, together with the C=C bond containing dipolarophiles, in the syntheses of 2-isoxazolines is presented. Methods for synthesizing isoxazolines (other than 1,3-DP cycloaddition) were also presented briefly. Various methods of nitrile oxide preparation, especially in situ-generated procedures, are presented. Special attention was paid to the application of various combinations of 1,3-DP cycloaddition with double bond migration (DBM) and with alkene metathesis (AM) in the syntheses of trisubstituted isoxazolines. Allyl compounds of the type QCH2CH=CH2 (Q = ArO, ArS, Ar, and others) play the role of dipolarophile precursors in the combinations of DPC mentioned, DBM and AM. Mechanistic aspects of cycloadditions, i.e., concerted or stepwise reaction mechanism and their regio- and stereoselectivity are also discussed from experimental and theoretical points of view. Side reactions accompanying cycloaddition, especially nitrile oxide dimerization, are considered. 2-Isoxazoline applications in organic synthesis and their biological activity, broad utility in medicine, agriculture, and other fields were also raised. Some remaining challenges in the field of 1,3-DP cycloaddition in the syntheses of isoxazolines are finally discussed.

Synthesis of the Macrolactone Cores of Maltepolides via a Diene-Ene Ring-Closing Metathesis Strategy.

Synthesis of the C19-truncated maltepolide E has been accomplished via a diene-ene ring-closing metathesis (RCM) strategy without damage to the C11-C14 alkenyl epoxy unit. Upon release of the C17-OH group, it attacked at the C14 position with double bond migration and epoxide ring opening to furnish the C19-truncated maltepolides A and B as proposed for the biosynthesis of maltepolides.

Allylic and Retro‐Allylic Rearrangements upon Bromination of 8,9‐Substituted 4,4,6‐Trimethyl‐4H‐Pyrrolo[3,2,1‐ij]Quinoline‐1,2‐Diones. New Aspects and Synthetic Applications

AbstractBromination of 4,4,6‐trimethyl‐4H‐pyrrolo[3,2,1‐ij]quinoline‐1,2‐diones containing an allylic moiety with N‐bromosuccinimide (NBS) in carbon tetrachloride in the presence of benzoyl peroxide (BPO) and in DMF solution were studied. When using an equimolar amount of NBS in the BPO‐CCl4 system, the reaction proceeds regioselectively and standardly at the methyl group at position 6 with the formation of 6‐bromomethylene derivatives. In the NBS‐DMF system, monobromination proceeds at position 5 with the migration of a multiple bond by the allylic rearrangement. With a twofold excess of NBS, in both cases a (Z)‐5‐bromo‐6‐bromomethylene derivative is formed. The 5‐monobromine isomers undergo retro‐allylic rearrangement in N‐ and S‐alkylation reactions, resulting exclusively in 6‐N‐alkyl and 6‐S‐alkyl derivatives, respectively. Similar products are formed by the same reactions with the use of 6‐bromomethylene derivatives.

Negligible Ion Migration in Tin‐Based and Tin‐Doped Perovskites

AbstractIon migration is a notorious phenomenon observed in ionic perovskite materials. It causes several severe issues in perovskite optoelectronic devices such as instability, current hysteresis, and phase segregation. Here, we report that, in contrast to lead halide perovskites (LHPs), no ion migration or phase segregation was observed in tin halide perovskites (THPs) under illumination or an electric field. The origin is attributed to a much stronger Sn‐halide bond and higher ion migration activation energy (Ea) in THPs, which remain nearly constant under illumination. We further figured out the threshold Ea for the absence of ion migration to be around 0.65 eV using the CsSnyPb1‐y(I0.6Br0.4)3 system whose Ea varies with Sn ratios. Our work shows that ion migration does not necessarily exist in all perovskites and suggests metallic doping to be a promising way of stopping ion migration and improving the intrinsic stability of perovskites.