Search results for "Cycloaddition"
showing 10 items of 392 documents
Use of Ambient Ionization High-Resolution Mass Spectrometry for the Kinetic Analysis of Organic Surface Reactions
2016
In contrast to homogeneous systems, studying the kinetics of organic reactions on solid surfaces remains a difficult task due to the limited availability of appropriate analysis techniques that are general, high-throughput, and capable of offering quantitative, structural surface information. Here, we demonstrate how direct analysis in real time mass spectrometry (DART-MS) complies with above considerations and can be used for determining interfacial kinetic parameters. The presented approach is based on the use of a MS tag that - in principle - allows application to other reactions. To show the potential of DART-MS, we selected the widely applied strain-promoted alkyne-azide cycloaddition …
Rapid and Complete Surface Modification with Strain-Promoted Oxidation-Controlled Cyclooctyne-1,2-Quinone Cycloaddition (SPOCQ)
2017
Abstract Strain‐promoted oxidation‐controlled cyclooctyne‐1,2‐quinone cycloaddition (SPOCQ) between functionalized bicyclo[6.1.0]non‐4‐yne (BCN) and surface‐bound quinones revealed an unprecedented 100 % conjugation efficiency. In addition, monitoring by direct analysis in real time mass spectrometry (DART‐MS) revealed the underlying kinetics and activation parameters of this immobilization process in dependence on its microenvironment.
Strain-Promoted Cycloaddition of Cyclopropenes with o-Quinones : A Rapid Click Reaction
2018
Abstract Novel click reactions are of continued interest in fields as diverse as bio‐conjugation, polymer science and surface chemistry. Qualification as a proper “click” reaction requires stringent criteria, including fast kinetics and high conversion, to be met. Herein, we report a novel strain‐promoted cycloaddition between cyclopropenes and o‐quinones in solution and on a surface. We demonstrate the “click character” of the reaction in solution and on surfaces for both monolayer and polymer brush functionalization.
ChemInform Abstract: Photochemical Transformations of Some Neoclerodane and Labdane Diterpene Ketones.
2010
Some neoclerodane (2–4) and labdane (5 and 6) diterpene ketones having a β- or γ-hydroxy function, an α-epoxy group, or an α-olefinic double bond have been irradiated at λ = 313 nm in dry solvents (benzene or methanol). Fruticolone (2) yielded the naturally occurring 5,6-seco-neoclerodan-6,1α-olide derivative fruticolide (1), while hispanolone (5) gave the δ-lactone 8, both transformations involving a Norrish type I photoreaction. The α,β-unsaturated ketone derivative 4 was transformed into 7 by a stereoselective intramolecular [2+2] cycloaddition reaction involving its furanic 13(16)-double bond. Finally, the α-epoxy ketone 6 was rearranged to the 10(98)abeo-labda-7,9-dione derivative 10. …
Visible-light photoredox catalyzed synthesis of pyrroloisoquinolines via organocatalytic oxidation/[3 + 2] cycloaddition/oxidative aromatization reac…
2014
Beilstein journal of organic chemistry 10, 1233-1238 (2014). doi:10.3762/bjoc.10.122
Limiting nuclearity in formation of polynuclear metal complexes through [2 + 3] cycloaddition: synthesis and magnetic properties of tri- and pentanuc…
2014
A tridentate ligand p-chloro-2-{(2-(dimethylamino)ethylimino)methyl}phenol (HL) was used to generate an octahedral nickel complex [Ni(L)Cl(H2O)2] 1 which was further converted into a square-planar nickel complex [Ni(L)(N3)] 2. The [2 + 3] cycloaddition reaction between metal coordinated azide 2 and different organonitriles under microwave irradiation afforded tri- and pentanuclear nickel(II) complexes 4a-4c. Reaction with benzonitrile and 3-cyano pyridine furnished the trinuclear species [Ni3L2(5-phenyltetrazolato)4(DMF)2] 4a and [Ni3L2{5-(3-pyridyl)-tetrazolato}4(DMF)2]·2H2O 4b, respectively. The nickel centers were found to be linearly disposed to each other and the complex is formed by a…
Selective Implantation of Diamines for Cooperative Catalysis in Isoreticular Heterometallic Titanium–Organic Frameworks
2021
[EN] We introduce the first example of isoreticular titanium-organic frameworks, MUV-10 and MUV-12, to show how the different affinity of hard Ti(IV) and soft Ca(II) metal sites can be used to direct selective grafting of amines. This enables the combination of Lewis acid titanium centers and available -NH, sites in two sizeable pores for cooperative cycloaddition of CO2 to epoxides at room temperature and atmospheric pressure. The selective grafting of molecules to heterometallic clusters adds up to the pool of methodologies available for controlling the positioning and distribution of chemical functions in precise positions of the framework required for definitive control of pore chemistr…
Hybrid catalysts for CO 2 conversion into cyclic carbonates
2019
The conversion of carbon dioxide into valuable chemicals such as cyclic carbonates is an appealing topic for the scientific community due to the possibility of valorizing waste into an inexpensive, available, nontoxic, and renewable carbon feedstock. In this regard, last-generation heterogeneous catalysts are of great interest owing to their high catalytic activity, robustness, and easy recovery and recycling. In the present review, recent advances on CO 2 cycloaddition to epoxide mediated by hybrid catalysts through organometallic or organo-catalytic species supported onto silica-, nanocarbon-, and metal-organic framework (MOF)-based heterogeneous materials, are highlighted and discussed.
Polycyclic aromatic chains on metals and insulating layers by repetitive [3+2] cycloadditions
2020
The vast potential of organic materials for electronic, optoelectronic and spintronic devices entails substantial interest in the fabrication of π-conjugated systems with tailored functionality directly at insulating interfaces. On-surface fabrication of such materials on non-metal surfaces remains to be demonstrated with high yield and selectivity. Here we present the synthesis of polyaromatic chains on metallic substrates, insulating layers, and in the solid state. Scanning probe microscopy shows the formation of azaullazine repeating units on Au(111), Ag(111), and h-BN/Cu(111), stemming from intermolecular homo-coupling via cycloaddition reactions of CN-substituted polycyclic aromatic az…
On-surface synthesis on a bulk insulator surface
2018
On-surface synthesis has rapidly emerged as a most promising approach to prepare functional molecular structures directly on a support surface. Compared to solution synthesis, performing chemical reactions on a surface offers several exciting new options: due to the absence of a solvent, reactions can be envisioned that are otherwise not feasible due to the insolubility of the reaction product. Perhaps even more important, the confinement to a two-dimensional surface might enable reaction pathways that are not accessible otherwise. Consequently, on-surface synthesis has attracted great attention in the last decade, with an impressive number of classical reactions transferred to a surface as…