4.3 1,3-Dipolar Cycloadditions of Alkenes

2022 ◽  
Author(s):  
D. Svatunek ◽  
K. N. Houk
Keyword(s):  
Click Reactions ◽  
Dipolar Cycloadditions ◽  
Wide Range

AbstractClick reactions between 1,3-dipoles and alkenes are appealing due to their versatility, which goes beyond simple conjugation applications and the synthesis of five-membered heterocycles. Leveraging various 1,3-dipoles and alkenes, photoactivatable, highly reactive, and “click to release” systems have been developed. In this article, we explore the wide range of reactivities, selectivities, and applications offered by this class of cycloadditions.

Improved Protocols for Microwave-Assisted Cu(I)-Catalyzed Huisgen 1,3-Dipolar Cycloadditions

2007 ◽  
Vol 72 (8) ◽  
pp. 1014-1024 ◽  
Author(s):  
Pedro Cintas ◽  
Katia Martina ◽  
Bruna Robaldo ◽  
Davide Garella ◽  
Luisa Boffa ◽  
...  
Keyword(s):  
Heterogeneous Catalysis ◽  
Microwave Irradiation ◽  
Ultrasound Irradiation ◽  
Conventional Heating ◽  
Dipolar Cycloaddition ◽  
One Pot ◽  
Click Reactions ◽  
Dipolar Cycloadditions ◽  
Microwave Assisted ◽  
New Applications

The Huisgen 1,3-dipolar cycloaddition of azides and acetylenes catalyzed by Cu(I) salts, leading to 1,2,3-triazoles, is one of the most versatile "click reactions". We have developed a series of optimized protocols and new applications of this reaction starting from several substrates, comparing heterogeneous vs homogeneous catalysis, conventional heating vs microwave irradiation or simultaneous microwave/ultrasound irradiation. Both non-conventional techniques strongly promoted the cycloaddition (bromide → azide → triazole), that could be conveniently performed in a one-pot procedure. This was feasible even with such bulky molecules as functionalized β-cyclodextrins (β-CD), starting from 61-O-tosyl-β-CD or from heptakis[6-O-(tert-butyldimethylsilyl)]-21-O-propargyl-β-CD. "Greener" heterogeneous catalysis with charcoal-supported Cu(II) or Cu(I) (prepared under ultrasound) was advantageously employed.

scholarly journals Copper nanoparticles on controlled pore glass (CPG) as highly efficient heterogeneous catalysts for “click reactions”

2020 ◽  
Vol 10 (1) ◽  
Author(s):  
Abdolrahim A. Rafi ◽  
Ismail Ibrahem ◽  
Armando Córdova
Keyword(s):  
Copper Nanoparticles ◽  
Heterogeneous Catalysts ◽  
Catalyst System ◽  
Terminal Alkynes ◽  
Click Reactions ◽  
Dipolar Cycloadditions ◽  
Organic Azides ◽  
Controlled Pore Glass ◽  
Pore Glass ◽  
High Yields

AbstractWe herein report that supported copper nanoparticles (CuNPs) on commercially available controlled pore glass (CPG), which exhibit high mechanical, thermal and chemical stability as compared to other silica-based materials, serve as a useful heterogeneous catalyst system for 1,3-dipolar cycloadditions (“click” reactions) between terminal alkynes and organic azides under green chemistry conditions. The supported CuNPs-CPG catalyst exhibited a broad substrate scope and gave the corresponding triazole products in high yields. The CuNPs-CPG catalyst exhibit recyclability and could be reuced multiple times without contaminating the products with Cu.

scholarly journals Multifunctional and Transformable ‘Clickable’ Hydrogel Coatings on Titanium Surfaces: From Protein Immobilization to Cellular Attachment

Polymers ◽  
2020 ◽  
Vol 12 (6) ◽  
pp. 1211
Author(s):  
Tugce Nihal Gevrek ◽  
Aysun Degirmenci ◽  
Rana Sanyal ◽  
Amitav Sanyal
Keyword(s):  
Alder Reaction ◽  
Diels Alder ◽  
Click Reactions ◽  
Ene Reaction ◽  
Diels Alder Reaction ◽  
Cellular Attachment ◽  
Wide Range ◽  
Hydrogel Coatings ◽  
Titanium Surfaces ◽  
Maleimide Group

Multifunctionalizable hydrogel coatings on titanium interfaces are useful in a wide range of biomedical applications utilizing titanium-based materials. In this study, furan-protected maleimide groups containing multi-clickable biocompatible hydrogel layers are fabricated on a titanium surface. Upon thermal treatment, the masked maleimide groups within the hydrogel are converted to thiol-reactive maleimide groups. The thiol-reactive maleimide group allows facile functionalization of these hydrogels through the thiol-maleimide nucleophilic addition and Diels–Alder cycloaddition reactions, under mild conditions. Additionally, the strained alkene unit in the furan-protected maleimide moiety undergoes radical thiol-ene reaction, as well as the inverse-electron-demand Diels–Alder reaction with tetrazine containing molecules. Taking advantage of photo-initiated thiol-ene ‘click’ reactions, we demonstrate spatially controlled immobilization of the fluorescent dye thiol-containing boron dipyrromethene (BODIPY-SH). Lastly, we establish that the extent of functionalization on hydrogels can be controlled by attachment of biotin-benzyl-tetrazine, followed by immobilization of TRITC-labelled ExtrAvidin. Being versatile and practical, we believe that the described multifunctional and transformable ‘clickable’ hydrogels on titanium-based substrates described here can find applications in areas involving modification of the interface with bioactive entities.

scholarly journals Synthesis of Triazoles by Electro-Assisted Click Reaction Using a Copper Foil Electrode

2021 ◽  
Author(s):  
Luceldi Carre-Rangel ◽  
Karla Espinoza ◽  
Mercedes Oropeza-Guzmán ◽  
Ignacio Rivero
Keyword(s):  
Copper Foil ◽  
Click Reaction ◽  
Reference Electrode ◽  
Process Efficiency ◽  
Water Medium ◽  
Click Reactions ◽  
Onset Potential ◽  
Wide Range ◽  
Biological Environment

This paper presents an innovative pathway for the synthesis of triazoles using the well-known “click chemistry” assisted by the electrochemical oxidation of metallic Cu0. The click reaction is used to couple a wide range of biological interest compounds. In this case, faster and less polluting methods for a biological environment was achived by in situ Cu0 electrooxidation, providing the suitable quantity of catalyst required by click reaction. The electrochemical cell was composed of a copper foil as the working electrode, a platinum wire serving as a counter electrode, and an Ag/AgCl wire as the reference electrode. Linear anodic sweep voltammetry in a tert-butanol-water medium (1:1), an electrolyte of tetrabutylammonium tetrafluoroborate (TBATFB), showed the onset potential of Cu0 electrooxidation. Using the same electrode configuration three different triazoles were prepared under constant electrode potential, in a short time (60 min), and splendid yields (78-90%). These results indicate that the in situ CuI formation occurs on the surface of the copper foil. A pulse potential program has also been implemented in which a yield of 92% was achieved, reducing electrode passivation and consequently increasing the process efficiency. The electroassisted click reactions are highly efficient to produce triazoles by an innovative electrochemical reaction. The products were characterized by infrared (IR), nuclear magnetic resonance (1H and 13C NMR), and mass spectrometry (MS).

Recent Applications of High Resolution Electron Microscopy to Crystalline Arrays of Virus Particles

1978 ◽  
Vol 36 (3) ◽  
pp. 470-482 ◽  
Author(s):  
R.W. Horne
Keyword(s):  
Electron Microscopy ◽  
Image Processing ◽  
Analytical Techniques ◽  
Staining Technique ◽  
High Resolution Electron Microscopy ◽  
Optical Diffraction ◽  
Full Potential ◽  
Virus Particles ◽  
Resolution Electron ◽  
Wide Range

The technique of surrounding virus particles with a neutralised electron dense stain was described at the Fourth International Congress on Electron Microscopy, Berlin 1958 (see Home & Brenner, 1960, p. 625). For many years the negative staining technique in one form or another, has been applied to a wide range of biological materials. However, the full potential of the method has only recently been explored following the development and applications of optical diffraction and computer image analytical techniques to electron micrographs (cf. De Hosier & Klug, 1968; Markham 1968; Crowther et al., 1970; Home & Markham, 1973; Klug & Berger, 1974; Crowther & Klug, 1975). These image processing procedures have allowed a more precise and quantitative approach to be made concerning the interpretation, measurement and reconstruction of repeating features in certain biological systems.

Microfabrication research at the National Submicron Facility

1983 ◽  
Vol 41 ◽  
pp. 86-89
Author(s):  
E.D. Wolf
Keyword(s):  
Integrated Circuits ◽  
Particle Physics ◽  
High Speed ◽  
New Technology ◽  
High Energy ◽  
High Energy Particle ◽  
New Science ◽  
Wide Range ◽  
Intermediate Domain ◽  
Circuit Function

Most microelectronics devices and circuits operate faster, consume less power, execute more functions and cost less per circuit function when the feature-sizes internal to the devices and circuits are made smaller. This is part of the stimulus for the Very High-Speed Integrated Circuits (VHSIC) program. There is also a need for smaller, more sensitive sensors in a wide range of disciplines that includes electrochemistry, neurophysiology and ultra-high pressure solid state research. There is often fundamental new science (and sometimes new technology) to be revealed (and used) when a basic parameter such as size is extended to new dimensions, as is evident at the two extremes of smallness and largeness, high energy particle physics and cosmology, respectively. However, there is also a very important intermediate domain of size that spans from the diameter of a small cluster of atoms up to near one micrometer which may also have just as profound effects on society as “big” physics.

Application of TEM to Deformation, Wear, and Fracture of Ceramics

1974 ◽  
Vol 32 ◽  
pp. 472-473
Author(s):  
B. J. Hockey
Keyword(s):  
Wear Resistance ◽  
High Temperature ◽  
Mechanical Behavior ◽  
Brittle Materials ◽  
High Temperature Strength ◽  
Wide Range ◽  
Corrosive Environments ◽  
Further Development

Ceramics, such as Al2O3 and SiC have numerous current and potential uses in applications where high temperature strength, hardness, and wear resistance are required often in corrosive environments. These materials are, however, highly anisotropic and brittle, so that their mechanical behavior is often unpredictable. The further development of these materials will require a better understanding of the basic mechanisms controlling deformation, wear, and fracture.The purpose of this talk is to describe applications of TEM to the study of the deformation, wear, and fracture of Al2O3. Similar studies are currently being conducted on SiC and the techniques involved should be applicable to a wide range of hard, brittle materials.

Observation of Atom Rows in Thorium Pyromellitate Using a Field Emission STEM

1977 ◽  
Vol 35 ◽  
pp. 80-81
Author(s):  
H. Todokoro ◽  
S. Nomura ◽  
T. Komoda
Keyword(s):  
Field Emission ◽  
Amorphous Carbon ◽  
Carbon Film ◽  
Dark Field Image ◽  
Dark Field ◽  
Amorphous Carbon Film ◽  
Atomic Size ◽  
Wide Range ◽  
A Chain

It is interesting to observe polymers at atomic size resolution. Some works have been reported for thorium pyromellitate by using a STEM (1), or a CTEM (2,3). The results showed that this polymer forms a chain in which thorium atoms are arranged. However, the distance between adjacent thorium atoms varies over a wide range (0.4-1.3nm) according to the different authors.The present authors have also observed thorium pyromellitate specimens by means of a field emission STEM, described in reference 4. The specimen was prepared by placing a drop of thorium pyromellitate in 10-3 CH3OH solution onto an amorphous carbon film about 2nm thick. The dark field image is shown in Fig. 1A. Thorium atoms are clearly observed as regular atom rows having a spacing of 0.85nm. This lattice gradually deteriorated by successive observations. The image changed to granular structures, as shown in Fig. 1B, which was taken after four scanning frames.

Development of a conical anode Fe-gun for low voltage SEM

1988 ◽  
Vol 46 ◽  
pp. 978-979
Author(s):  
T. Miyokawa ◽  
S. Norioka ◽  
S. Goto
Keyword(s):  
High Resolution ◽  
Field Emission ◽  
Low Voltage ◽  
Irradiation Damage ◽  
Cold Cathode ◽  
Virtual Source ◽  
Source Position ◽  
Electrostatic Lens ◽  
Electrostatic Lenses ◽  
Wide Range

Field emission SEMs (FE-SEMs) are becoming popular due to their high resolution needs. In the field of semiconductor product, it is demanded to use the low accelerating voltage FE-SEM to avoid the electron irradiation damage and the electron charging up on samples. However the accelerating voltage of usual SEM with FE-gun is limited until 1 kV, which is not enough small for the present demands, because the virtual source goes far from the tip in lower accelerating voltages. This virtual source position depends on the shape of the electrostatic lens. So, we investigated several types of electrostatic lenses to be applicable to the lower accelerating voltage. In the result, it is found a field emission gun with a conical anode is effectively applied for a wide range of low accelerating voltages.A field emission gun usually consists of a field emission tip (cold cathode) and the Butler type electrostatic lens.

Comparison of Deterministic and Linear Cosine Spatial Filtering of Transmission Electron Micrographs

1972 ◽  
Vol 30 ◽  
pp. 596-597
Author(s):  
David A. Ansley
Keyword(s):  
Spherical Aberration ◽  
Focal Length ◽  
Chromatic Aberration ◽  
Spatial Filter ◽  
Operating Conditions ◽  
Objective Lens ◽  
List Type ◽  
Spatial Filters ◽  
Transmission Electron ◽  
Wide Range

The coherence of the electron flux of a transmission electron microscope (TEM) limits the direct application of deconvolution techniques which have been used successfully on unmanned spacecraft programs. The theory assumes noncoherent illumination. Deconvolution of a TEM micrograph will, therefore, in general produce spurious detail rather than improved resolution.A primary goal of our research is to study the performance of several types of linear spatial filters as a function of specimen contrast, phase, and coherence. We have, therefore, developed a one-dimensional analysis and plotting program to simulate a wide 'range of operating conditions of the TEM, including adjustment of the:(1) Specimen amplitude, phase, and separation(2) Illumination wavelength, half-angle, and tilt(3) Objective lens focal length and aperture width(4) Spherical aberration, defocus, and chromatic aberration focus shift(5) Detector gamma, additive, and multiplicative noise constants(6) Type of spatial filter: linear cosine, linear sine, or deterministic

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