Organic Reactivity Control by Means of Neighboring Groups and Organometallics. A Personal Account

1994 ◽  
Vol 59 (1) ◽  
pp. 1-74 ◽  
Author(s):  
Pavel Kočovský

This review summarizes the main topics of our research and covers the period of the last 15 years. The prime interest is focused on various ways of controlling the regio- and stereoselectivity of selected organic reactions, in particular electrophilic additions, cleavage of cyclopropane rings, and allylic substitutions by means of neighboring groups and/or transition and non-transition metals. In the first part, the factors governing the course of electrophilic additions are assessed, culminating in the formulation of selection rules for the reactivity of cyclohexene systems, and in a concise synthesis of the natural cardioactive drug, strophanthidin. These studies also contribute to a better understanding of the mechanisms of electrophilic additions. The second part describes recent developments in the stereo- and regiocontrolled cleavage of cyclopropane rings by non-transition metals (Tl and Hg), and the reactivity and transmetalation (with Pd) of the primary products. This methodology has resulted in novel routes to unique polycyclic structures, and will have synthetic applications in the near future. Evidence for the stereospecific "corner" cleavage of the cyclopropane ring has been provided for the first time for Tl and later for Hg. The third part deals with transition metal-catalyzed allylic substitution. Evidence for a new "syn" mechanism for the formation of the intermediate (π-allyl)palladium complex has been provided, which runs counter to the generally accepted "anti" mechanism. A novel method for a Pd-catalyzed allylic oxidation has been developed and employed in the synthesis of natural sesquiterpenes. The increasing importance of transition and non-transition metals for synthetic organic chemistry is demonstrated by their unique reactivity in a number of the papers included in this review.

Author(s):  
W.J. de Ruijter ◽  
P. Rez ◽  
David J. Smith

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.


Author(s):  
S.J. Krause ◽  
W.W. Adams

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.


2018 ◽  
pp. 47-52

Epimedium elatum (Morren & Decne) of family Berberidaceace is a rare perennial medicinal plant, endemic to high altitude forests of Northwestern Himalayas in India. Ethnobotanically, it has been used as an ingredient for treatment of bone-joint disorders, impotence and kidney disorders in Kashmir Himalayas. Phytochemically, it is rich in Epimedin ABC and Icariin; all of these have been demonstrated to possess remarkable biological activities like PDE-5 inhibition (treatment of erectile dysfunction), anticancer, antiosteoporosis antioxidant and antiviral properties. The present investigation reports its traditional usage, comprehensive distribution and conservation status from twenty ecogeographical regions in Kashmir Himalayas, India. The species was reported from Gurez valley for the first time. Numerous threats like excessive grazing, deforestration, habitat fragmentation, tourism encroachment, landslides and excessive exploitation have decreased its natural populations in most of the surveyed habitats. Consequently, its existence may become threatened in near future if timely conservation steps are not taken immediately by concerned stakeholders involved in medicinal plant research. Moreover, use of plant tissue culture techniques is recommended for development of its in vitro propagation protocols. Therefore, introduction of this medicinal plant in botanical gardens, protected sites and development of monitoring programmes are needed for its immediate conservation in Northwestern Himalayas, India.


Author(s):  
Bing Yan

This chapter overviews Chinese reception of Milton, with an emphasis on some of the most well-known Chinese translations of Paradise Lost. Close readings of these translations against Milton’s original demonstrate the difficulties of and resolutions for rendering Milton’s verse specific to Chinese. The subsequent discussion of the paratexts accompanying Chinese translations and of ‘introduction to world literature’ series gives a sense of the collaborative context that has shaped and continues to shape today’s general reception of Milton in China. That politically charged reception, eager to view Milton’s Satan as the embodiment of the poet’s revolutionary spirit, also dominates some recent works of Chinese literary criticism. The chapter ends by conceding that, while Milton scholarship in China has been relatively univocal and is still young, recent developments in world literature promise that innovative and intriguing work on Milton can be expected from China in the near future.


The recycling and reuse of materials and objects were extensive in the past, but have rarely been embedded into models of the economy; even more rarely has any attempt been made to assess the scale of these practices. Recent developments, including the use of large datasets, computational modelling, and high-resolution analytical chemistry, are increasingly offering the means to reconstruct recycling and reuse, and even to approach the thorny matter of quantification. Growing scholarly interest in the topic has also led to an increasing recognition of these practices from those employing more traditional methodological approaches, which are sometimes coupled with innovative archaeological theory. Thanks to these efforts, it has been possible for the first time in this volume to draw together archaeological case studies on the recycling and reuse of a wide range of materials, from papyri and textiles, to amphorae, metals and glass, building materials and statuary. Recycling and reuse occur at a range of site types, and often in contexts which cross-cut material categories, or move from one object category to another. The volume focuses principally on the Roman Imperial and late antique world, over a broad geographical span ranging from Britain to North Africa and the East Mediterranean. Last, but not least, the volume is unique in focusing upon these activities as a part of the status quo, and not just as a response to crisis.


2019 ◽  
Vol 15 (S356) ◽  
pp. 225-225
Author(s):  
Dalya Baron

AbstractIn this talk I will show that multi-wavelength observations can provide novel constraints on the properties of ionized gas outflows in AGN. I will present evidence that the infrared emission in active galaxies includes a contribution from dust which is mixed with the outflow and is heated by the AGN. We detect this infrared component in thousands of AGN for the first time, and use it to constrain the outflow location. By combining this with optical emission lines, we constrain the mass outflow rates and energetics in a sample of 234 type II AGN, the largest such sample to date. The key ingredient of our new outflow measurements is a novel method to estimate the electron density using the ionization parameter and location of the flow. The inferred electron densities, ∼104.5 cm−3, are two orders of magnitude larger than found in most other cases of ionized outflows. We argue that the discrepancy is due to the fact that the commonly-used [SII]-based method underestimates the true density by a large factor. As a result, the inferred mass outflow rates and kinetic coupling efficiencies are 1–2 orders of magnitude lower than previous estimates, and 3–4 orders of magnitude lower than the typical requirement in hydrodynamic cosmological simulations. These results have significant implications for the relative importance of ionized outflows feedback in this population.


RSC Advances ◽  
2021 ◽  
Vol 11 (13) ◽  
pp. 7146-7179
Author(s):  
P. V. Saranya ◽  
Mohan Neetha ◽  
Thaipparambil Aneeja ◽  
Gopinathan Anilkumar

Spirooxindoles are used as anticancer-, antiviral-, antimicrobial agents etc. The use of transition metals as catalysts for the synthesis of spirooxindoles is advancing rapidly. Here, we focus on recent advances in transition metal-catalyzed synthesis of spirooxindoles.


2018 ◽  
Vol 47 (11) ◽  
pp. 3861-3898 ◽  
Author(s):  
Vsevolod A. Peshkov ◽  
Olga P. Pereshivko ◽  
Anton A. Nechaev ◽  
Anatoly A. Peshkov ◽  
Erik V. Van der Eycken

This focused review aims to summarize recent developments in the processes involving additions of secondary propargylamines to various heteroallenes and subsequent transition metal-catalyzed or electrophile-mediated cyclizations.


1988 ◽  
Vol 66 (9) ◽  
pp. 2219-2228 ◽  
Author(s):  
John M. Goodings ◽  
Quang Tran ◽  
Nicholas S. Karellas

The same fuel-rich, premixed, conical, methane–oxygen flame at 2200 K and atmospheric pressure used for studies of Fe, Co, Ni, Cu, and Zn in Part I (1) is doped with the same concentration (~1 ppm) of Sc, Ti, V, Cr, and Mn to complete the first row of ten transition metals. Metallic ions of these metals and their compounds formed by chemical ionization reactions with H3O+ are observed by sampling the flame through a nozzle into a quadrupole mass spectrometer. Concentration profiles of individual and total cations are measured as a function of distance along the flame axis, and also mass spectra at a fixed point in the burnt gas. If A is the metal atom, the observed ions can be represented by four hydrate series including (a) A+•nH2O, (b) AOH+•nH2O, (c) AO+•nH2O, and (d) AO2H+•nH2O with n = 0–3 or 4, giving a maximum of four ligands around the metal atom. However, alternative isomeric structures are possible for each of the four basic series (e.g. AO+•2H2O ~ A(OH)2+•H2O ~ A(OH)3H+). The ions observed with Cr and Mn, in common with those of Fe, Co, Ni, and Cu, strongly favour series (a). On the other hand, Sc is completely different; the ions of series (c) are dominant. All four series are observed with each of Ti and V. Series (b) dominates for Ti and series (c) for V; ions from series (d) were observed for the first time. The ion chemistry of these metals is discussed in detail with emphasis on the probable chemical ionization reactions responsible for metallic ion formation. The pre-eminent role of proton transfer processes is apparent.


2021 ◽  
Vol 18 (1) ◽  
Author(s):  
Manuela Temmer

AbstractThe Sun, as an active star, is the driver of energetic phenomena that structure interplanetary space and affect planetary atmospheres. The effects of Space Weather on Earth and the solar system is of increasing importance as human spaceflight is preparing for lunar and Mars missions. This review is focusing on the solar perspective of the Space Weather relevant phenomena, coronal mass ejections (CMEs), flares, solar energetic particles (SEPs), and solar wind stream interaction regions (SIR). With the advent of the STEREO mission (launched in 2006), literally, new perspectives were provided that enabled for the first time to study coronal structures and the evolution of activity phenomena in three dimensions. New imaging capabilities, covering the entire Sun-Earth distance range, allowed to seamlessly connect CMEs and their interplanetary counterparts measured in-situ (so called ICMEs). This vastly increased our knowledge and understanding of the dynamics of interplanetary space due to solar activity and fostered the development of Space Weather forecasting models. Moreover, we are facing challenging times gathering new data from two extraordinary missions, NASA’s Parker Solar Probe (launched in 2018) and ESA’s Solar Orbiter (launched in 2020), that will in the near future provide more detailed insight into the solar wind evolution and image CMEs from view points never approached before. The current review builds upon the Living Reviews article by Schwenn from 2006, updating on the Space Weather relevant CME-flare-SEP phenomena from the solar perspective, as observed from multiple viewpoints and their concomitant solar surface signatures.


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