Search results for "alkenes"
showing 10 items of 50 documents
Modular one-pot synthesis of tetrasubstituted pyrroles from alpha-(alkylideneamino)nitriles.
2007
2,3,4,5-Tetrasubstituted pyrroles have been prepared with high regioselectivity by a formal cycloaddition of alpha-(alkylideneamino)nitriles and nitroolefins followed by elimination of HCN and HNO2. The reaction allows the convergent construction of the pyrrole ring in four steps from a nitroalkane and three aldehydes.
The Participation of 3,3,3-Trichloro-1-nitroprop-1-ene in the [3 + 2] Cycloaddition Reaction with Selected Nitrile N-Oxides in the Light of the Exper…
2021
The regioselective zw-type [3 + 2] cycloaddition (32CA) reactions of a series of aryl-substituted nitrile N-oxides (NOs) with trichloronitropropene (TNP) have been both experimentally and theoretically studied within the Molecular Electron Density Theory (MEDT). Zwitterionic NOs behave as moderate nucleophiles while TNP acts as a very strong electrophile in these polar 32CA reactions of forward electron density flux, which present moderate activation Gibbs free energies of 22.8–25.6 kcal·mol−1 and an exergonic character of 28.4 kcal·mol−1 that makes them irreversible and kinetically controlled. The most favorable reaction is that involving the most nucleophilic MeO-substituted NO. Despite P…
A Stereocontrolled Protocol to Highly Functionalized Fluorinated Scaffolds through a Fluoride Opening of Oxiranes
2016
A novel selective and substrate-dependent synthetic protocol has been developed towards the synthesis of various fluorine-containing, highly functionalized cycloalkane derivatives. The method involves the stereoselective epoxidation of some unsaturated cyclic beta-amino acid derivatives as model compounds, followed by a regioselective fluoride opening of oxiranes under various conditions with Deoxofluor and XtalFluor-E reagents, thereby offering an insight into this new epoxide opening methodology with fluoride.
2-Alkenoyl Pyridine N-Oxides, Highly Efficient Dienophiles for the Enantioselective Cu(II)−Bis(oxazoline) Catalyzed Diels−Alder Reaction
2007
2-Alkenoyl pyridine N-oxides are introduced as a new kind of efficient dienophiles for the Cu(II)−bis(oxazoline) (BOX) catalyzed enantioselective Diels−Alder reaction affording higher reactivity and enantioselectivity (ee's up to 96%) than the corresponding nonoxidized 2-alkenoyl pyridines.
SPM and TOF-SIMS investigation of the physical and chemical modification induced by tip writing of self-assembled monolayers
2003
Abstract The nanoelectrochemical modification of alkyl self-assembled monolayers (SAMs) obtained on hydrogenated silicon surfaces via radical-initiated reactions of 1-octadecene has been investigated. Scanning Probe Microscopy (SPM) showed that the modification of the organic layer occurs by applying either positive or negative biases to the tip at a threshold of about ±5 V. When the bias absolute value was ≤6 V, the height of the monolayer was only faintly modified, whereas a consistent increase in tip/sample friction force was observed, in agreement with the formation of hydrophilic moieties at the organic surface. In addition to the increase of friction, bias absolute values larger than …
How do cuticular hydrocarbons evolve? Physiological constraints and climatic and biotic selection pressures act on a complex functional trait
2017
Cuticular hydrocarbons (CHCs) cover the cuticles of virtually all insects, serving as a waterproofing agent and as a communication signal. The causes for the high CHC variation between species, and the factors influencing CHC profiles, are scarcely understood. Here, we compare CHC profiles of ant species from seven biogeographic regions, searching for physiological constraints and for climatic and biotic selection pressures. Molecule length constrained CHC composition: long-chain profiles contained fewer linear alkanes, but more hydrocarbons with disruptive features in the molecule. This is probably owing to selection on the physiology to build a semi-fluid cuticular layer, which is necessa…
Influence of nitric oxide on the generation and repair of oxidative DNA damage in mammalian cells
2002
We have analysed the effects of endogenously and exogenously generated nitric oxide (NO) in cultured mammalian fibroblasts on: (i) the steady-state (background) levels of oxidative DNA base modifications; (ii) the susceptibility of the cells to the induction of additional DNA damage and micronuclei by H(2)O(2); and (iii) the repair kinetics of various types of DNA modifications. Steady-state levels of oxidative DNA base modifications, measured by means of an alkaline elution assay in combination with the repair endonuclease Fpg protein, were similar in NO-overproducing B6 mouse fibroblasts stably transfected with an inducible NO synthase (iNOS) and in control cells. Increased oxidative dama…
Keggin heteropolyacid H3PW12O40 supported on different oxides for catalytic and catalytic photo-assisted propene hydration
2013
Catalytic and catalytic photo-assisted hydration of propene to form 2-propanol in gas–solid regime at atmospheric pressure and 85 1C were carried out by using a heteropolyacid (POM) supported on different oxides. Binary materials were prepared by impregnation of H3PW12O40 on different commercial and home prepared supports (TiO2, SiO2, WO3, ZrO2, ZnO, Al2O3). Some of the composites were active both for catalytic and catalytic photo-assisted reactions. The Keggin type POM was completely and partially degraded, when supported on ZnO and Al2O3, respectively, and these binary solids always resulted as inactive for both catalytic and catalytic photo-assisted reactions. The supported Keggin POM sp…
End Capping Ring-Opening Olefin Metathesis Polymerization Polymers with Vinyl Lactones
2008
The selective placement of a functional group at the chain end of a ring-opening metathesis polymer using ruthenium carbene initiators has been a significant limitation. Here we demonstrate a highly effective and facile end-capping technique for ROMP with living ruthenium carbene chain ends using single-turnover olefin metathesis substrates. Vinylene carbonate and 3H-furanone are introduced as functionalization and termination agents for the ruthenium-initiated ring-opening metathesis polymerization. This leads directly to the formation of functional polymer end groups without further chemical transformation steps. Aldehyde and carboxylic acid end groups can be introduced by this new method…
Iodofluorination of alkenes and alkynes promoted by iodine and 4-iodotoluene difluoride
2006
It was found that a mixt. of mol. iodine and 4-iodotoluene difluoride are useful to generate in situ the electrophilic iodine/nucleophilic fluorine (IF) couple that was able to add in a Markovnikov fashion and with prevalent anti-stereoselectivity to various alkenes and alkynes.