Hydrogen Atom Donors: Recent Developments

2011 ◽  
pp. 93-120 ◽  
Author(s):  
Andreas Gansäuer ◽  
Lei Shi ◽  
Matthias Otte ◽  
Inga Huth ◽  
Antonio Rosales ◽  
...  
Keyword(s):  
Hydrogen Atom ◽  
Recent Developments

Site-selective C(sp3)-H Functionalizations Mediated by Hydrogen Atom Transfer Reactions via α-Amino/α-Amido Radicals

Synthesis ◽  
2021 ◽  
Author(s):  
Jaspreet Kaur ◽  
Joshua Philip Barham
Keyword(s):  
Hydrogen Atom ◽  
Three Dimensional ◽  
Hydrogen Atom Transfer ◽  
Dimensional Structure ◽  
Atom Transfer ◽  
Bond Polarity ◽  
Recent Developments ◽  
A Site ◽  
Site Selective ◽  
And Control

Amines and amides, as N-containing compounds, are ubiquitous in pharmaceutically active scaffolds, natural products, agrochemicals and peptides. Amides in nature bear key responsibility for three-dimensional structure, such as in proteins. Structural modifications to amines and amides, especially at their positions α- to N, bring about profound changes in biological activity oftentimes leading to more desirable pharmacological profiles of small molecule drugs. A number of recent developments in synthetic methodology for the functionalizations of amines and amides omit the need of directing groups or pre-functionalizations, achieving direct activation of the otherwise benign C(sp3)-H bond. Among these, hydrogen atom transfer (HAT) has proven a very powerful platform for the selective activation of amines and amides to their α-amino and α-amido radicals, which can then be employed to furnish C-C and C-X (X=heteroatom) bonds. The ability to both form these radicals and control their reactivity in a site-selective manner is of utmost importance for such chemistries to witness applications in late-stage functionalization. Therefore, this review captures contemporary HAT strategies to realize chemo- and regioselective amine and amide α-C(sp3)-H functionalization, based on bond strength, bond polarity, reversible HAT equilibria, traceless electrostatic directing auxiliaries and steric effects of in situ-generated HAT agents.

ChemInform Abstract: Hydrogen Atom Donors: Recent Developments

ChemInform ◽  
2013 ◽  
Vol 44 (16) ◽  
pp. no-no
Author(s):  
Andreas Gansaeuer ◽  
Lei Shi ◽  
Matthias Otte ◽  
Inga Huth ◽  
Antonio Rosales ◽  
...  
Keyword(s):  
Hydrogen Atom ◽  
Recent Developments

scholarly journals Tris(acetylacetonato) Iron(III): Recent Developments and Synthetic Applications

Synthesis ◽  
2018 ◽  
Vol 51 (01) ◽  
pp. 161-177 ◽  
Author(s):  
Dennis Lübken ◽  
Marius Saxarra ◽  
Markus Kalesse
Keyword(s):  
Hydrogen Atom ◽  
Natural Product ◽  
Cross Coupling ◽  
Short Review ◽  
Hydrogen Atom Transfer ◽  
Atom Transfer ◽  
Coupling Reactions ◽  
Total Syntheses ◽  
Cross Coupling Reactions ◽  
Recent Developments

Tris(acetylacetonato) iron(III) [Fe(acac)3] is an indispensable reagent in synthetic chemistry. Its applications range from hydrogen atom transfer to cross-coupling reactions and to use as a Lewis acid. Consequently, the exceptional utility of Fe(acac)3 has been demonstrated in several total syntheses. This short review summarizes the applications of Fe(acac)3 in methodology and catalysis and highlights its use for the synthesis of medicinally relevant structures and in natural product syntheses.1 Introduction2 Hydrogen Atom Transfer (HAT)3 Oxidations and Radical Transformations4 Synthesis and Use of Alkynes and Allenes5 Cross-Couplings and Cycloisomerizations6 Borylations7 Miscellaneous Reactions8 Conclusions

Hydrogen in Nanostructured, Carbon-Related, and Metallic Materials

MRS Bulletin ◽  
2002 ◽  
Vol 27 (9) ◽  
pp. 705-711 ◽  
Author(s):  
Andreas Züttel ◽  
Shin-ichi Orimo
Keyword(s):  
Hydrogen Atom ◽  
Carbon Atom ◽  
Hydrogen Adsorption ◽  
Theoretical Calculations ◽  
High Surface ◽  
High Surface Area ◽  
Metallic Materials ◽  
Hydrogen Atoms ◽  
Hydrogen Interaction ◽  
Recent Developments

AbstractRecent developments in hydrogen interaction with carbonaceous materials are reviewed in this article. The interaction is based on van der Waals attractive forces (physisorption), or the overlap of the highest occupied molecular orbitals of carbon with the hydrogen electron, overcoming the activation-energy barrier for hydrogen dissociation (chemisorption). While the physisorption of hydrogen limits the hydrogen-to-carbon ratio to less than one hydrogen atom per two carbon atoms (i.e., 4.2 mass%), in chemisorption, a ratio of two hydrogen atoms per one carbon atom is realized (e.g., in polyethylene). However, the materials with large hydrogen-to-carbon ratios only liberate the hydrogen at elevated temperature. No evidence, apart from theoretical calculations, was found for a new hydrogen-adsorption phenomenon on carbon nanotubes (CNTs), as compared with high-surface-area graphite. The curvature of CNTs and fullerenes increases the reactivity of these materials with hydrogen and leads more easily to the formation of hydrocarbons, as compared with graphite. Nanocrystalline or amorphous carbon exhibits an intermediate state for hydrogen between physisorption and chemisorption and absorbs up to one hydrogen atom per carbon atom. Nanostructured carbonaceous and metallic materials offer a large potential for hydrogen storage and must therefore be investigated in more detail.

Trends in Electron Energy Loss Spectroscopy

1977 ◽  
Vol 35 ◽  
pp. 228-229
Author(s):  
C. Colliex ◽  
P. Trebbia
Keyword(s):  
Energy Loss ◽  
Electron Energy ◽  
Electron Energy Loss Spectroscopy ◽  
Materials Science ◽  
Analytical Technique ◽  
Recent Developments ◽  
Quantitative Results ◽  
Electron Microscopes ◽  
Electron Energy Loss ◽  
Primary Electrons

The physical foundations for the use of electron energy loss spectroscopy towards analytical purposes, seem now rather well established and have been extensively discussed through recent publications. In this brief review we intend only to mention most recent developments in this field, which became available to our knowledge. We derive also some lines of discussion to define more clearly the limits of this analytical technique in materials science problems.The spectral information carried in both low ( 0<ΔE<100eV ) and high ( >100eV ) energy regions of the loss spectrum, is capable to provide quantitative results. Spectrometers have therefore been designed to work with all kinds of electron microscopes and to cover large energy ranges for the detection of inelastically scattered electrons (for instance the L-edge of molybdenum at 2500eV has been measured by van Zuylen with primary electrons of 80 kV). It is rather easy to fix a post-specimen magnetic optics on a STEM, but Crewe has recently underlined that great care should be devoted to optimize the collecting power and the energy resolution of the whole system.

Filaments and membranes in the mitotic apparatus

1983 ◽  
Vol 41 ◽  
pp. 544-547
Author(s):  
Kent McDonald
Keyword(s):  
Intermediate Filaments ◽  
Mitotic Spindle ◽  
Mitotic Apparatus ◽  
Light Microscope Level ◽  
Microtubule Associated Proteins ◽  
Recent Developments ◽  
Associated Proteins ◽  
Force Generator ◽  
Spindle Function ◽  
Antibody Technology

At the light microscope level the recent developments and interest in antibody technology have permitted the localization of certain non-microtubule proteins within the mitotic spindle, e.g., calmodulin, actin, intermediate filaments, protein kinases and various microtubule associated proteins. Also, the use of fluorescent probes like chlorotetracycline suggest the presence of membranes in the spindle. Localization of non-microtubule structures in the spindle at the EM level has been less rewarding. Some mitosis researchers, e.g., Rarer, have maintained that actin is involved in mitosis movements though the bulk of evidence argues against this interpretation. Others suggest that a microtrabecular network such as found in chromatophore granule movement might be a possible force generator but there is little evidence for or against this view. At the level of regulation of spindle function, Harris and more recently Hepler have argued for the importance of studying spindle membranes. Hepler also believes that membranes might play a structural or mechanical role in moving chromosomes.

Software pattern recognition applied to nanodiffraction patterns from a STEM instrument

1986 ◽  
Vol 44 ◽  
pp. 694-695
Author(s):  
G.Y. Fan ◽  
J.M. Cowley
Keyword(s):  
Image Processing ◽  
Pattern Recognition ◽  
Computer Software ◽  
Processing System ◽  
Light Level ◽  
Host Computer ◽  
Low Light ◽  
Image Processing System ◽  
Recent Developments ◽  
On Line

In recent developments, the ASU HB5 has been modified so that the timing, positioning, and scanning of the finely focused electron probe can be entirely controlled by a host computer. This made the asynchronized handshake possible between the HB5 STEM and the image processing system which consists of host computer (PDP 11/34), DeAnza image processor (IP 5000) which is interfaced with a low-light level TV camera, array processor (AP 400) and various peripheral devices. This greatly facilitates the pattern recognition technique initiated by Monosmith and Cowley. Software called NANHB5 is under development which, instead of employing a set of photo-diodes to detect strong spots on a TV screen, uses various software techniques including on-line fast Fourier transform (FFT) to recognize patterns of greater complexity, taking advantage of the sophistication of our image processing system and the flexibility of computer software.

High-resolution microscopy of twin boundaries in gold

1987 ◽  
Vol 45 ◽  
pp. 260-261
Author(s):  
William Krakow ◽  
David A. Smith
Keyword(s):  
High Resolution ◽  
Specimen Preparation ◽  
Gold Films ◽  
Boundary Area ◽  
Transmission Electron ◽  
Recent Developments ◽  
Tilt Boundaries ◽  
High Resolution Microscopy ◽  
Twist Boundaries

Recent developments in specimen preparation, imaging and image analysis together permit the experimental determination of the atomic structure of certain, simple grain boundaries in metals such as gold. Single crystal, ∼125Å thick, (110) oriented gold films are vapor deposited onto ∼3000Å of epitaxial silver on (110) oriented cut and polished rock salt substrates. Bicrystal gold films are then made by first removing the silver coated substrate and placing in contact two suitably misoriented pieces of the gold film on a gold grid. Controlled heating in a hot stage first produces twist boundaries which then migrate, so reducing the grain boundary area, to give mixed boundaries and finally tilt boundaries perpendicular to the foil. These specimens are well suited to investigation by high resolution transmission electron microscopy.

Recent developments in automated Transmission Electron MI

1989 ◽  
Vol 47 ◽  
pp. 46-47
Author(s):  
W.J. de Ruijter ◽  
P. Rez ◽  
David J. Smith
Keyword(s):  
Image Analysis ◽  
Computer Image ◽  
Lens Design ◽  
Computer Image Analysis ◽  
Transmission Electron ◽  
Resolution Electron ◽  
Recent Developments ◽  
On Line ◽  
Routine Procedures ◽  
Near Future

There is growing interest in the on-line use of computers in high-resolution electron n which should reduce the demands on highly skilled operators and thereby extend the r of the technique. An on-line computer could obviously perform routine procedures hand, or else facilitate automation of various restoration, reconstruction and enhan These techniques are slow and cumbersome at present because of the need for cai micrographs and off-line processing. In low resolution microscopy (most biologic; primary incentive for automation and computer image analysis is to create a instrument, with standard programmed procedures. In HREM (materials researc computer image analysis should lead to better utilization of the microscope. Instru (improved lens design and higher accelerating voltages) have improved the interpretab the level of atomic dimensions (approximately 1.6 Å) and instrumental resolutior should become feasible in the near future.

Recent developments in low-voltage SEM of polymers

1993 ◽  
Vol 51 ◽  
pp. 866-867
Author(s):  
S.J. Krause ◽  
W.W. Adams
Keyword(s):  
Low Voltage ◽  
Chromatic Aberration ◽  
Thermal Electron ◽  
Analytical Technique ◽  
Recent Developments ◽  
Beam Currents ◽  
New Generation ◽  
First Time ◽  
Voltage Scanning ◽  
Beam Damage

Over the past decade low voltage scanning electron microscopy (LVSEM) of polymers has evolved from an interesting curiosity to a powerful analytical technique. This development has been driven by improved instrumentation and in particular, reliable field emission gun (FEG) SEMs. The usefulness of LVSEM has also grown because of an improved theoretical and experimental understanding of sample-beam interactions and by advances in sample preparation and operating techniques. This paper will review progress in polymer LVSEM and present recent results and developments in the field.In the early 1980s a new generation of SEMs produced beam currents that were sufficient to allow imaging at low voltages from 5keV to 0.5 keV. Thus, for the first time, it became possible to routinely image uncoated polymers at voltages below their negative charging threshold, the "second crossover", E2 (Fig. 1). LVSEM also improved contrast and reduced beam damage in sputter metal coated polymers. Unfortunately, resolution was limited to a few tenths of a micron due to the low brightness and chromatic aberration of thermal electron emission sources.

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