New Lewis-basic N-oxides as chiral organocatalysts in asymmetric allylation of aldehydes

Allylation of aromatic and heteroaromatic aldehydes 1a-k with allyltrichlorosilane 2 can be catalyzed by the new heterobidentate, terpene-derived bipyridine N-monoxides 4, 6a,b, and 8-11 (相似文献   

Fragmentation and reactions of two isomeric O-alkyl S-(2-dialkylamino)ethyl methylphosphonothiolates studied by electrospray ionization/ion trap mass spectrometry

An initial investigation into the electrospray ionization ion trap mass spectrometry (ESI/ITMS) of simple organophosphorus compounds [1] demonstrated that detailed structural information could be obtained by sequential fragmentation of the ions using collision induced dissociation (CID). Several novel fragmentations/rearrangements were observed and it was apparent that the full potential of this approach could not be exploited until a more detailed understanding of the ion fragmentations was obtained. Such an understanding will only result from a detailed study of a wide range of compounds. The present paper describes the investigation of two isomeric organophosphates of particular relevance to chemical warfare convention (CWC) considerations.     

A study of the redox properties of MoOx/SiO2

A sample of MoOx/SiO2, in which all of the Mo cations are present as isolated mono-oxo molybdate moieties, was prepared and investigated to understand the redox chemistry of such molybdate species and their ability to exchange oxygen with O2 and H2O. Raman spectroscopy was used to monitor the exchange of 18O for 16O in the Mo=O bond of isolated molybdate species, whereas mass spectrometry was used to follow the isotopic composition of the gaseous species, i.e., O2 and H2O. Reduction in H2 at 920 K results in the loss of one O atom per Mo atom, and consistent with this, all of the Mo(VI) cations are reduced to Mo(IV) cations. Raman spectroscopy shows that virtually all Mo=O bonds of the original molybdate species are lost upon reduction. While reoxidation of Mo(IV) cations by O2 is quantitative, studies using 18O2 reveal that only a small part of the newly formed Mo=O bonds are 18O labeled, and that the balance are 16O labeled, indicating that O-atom exchange between the support, SiO2, and the supported MoOx species occurs during reoxidation. Rapid exchange of O atoms was observed upon exposure of both bare SiO2 and MoOx/SiO2 to H2(18)O at 920 K, and the presence of MoOx species was found to enhance the rate of exchange. By contrast, very slow exchange of O atoms was observed when the oxidized catalyst was exposed to 18O2 at 920 K. In situ observations of the catalyst during exposure to a mixture of H2 and 18O2 at 920 K showed that all of the Mo cations remained in the VI oxidation state and that O atom exchange occurred at a rate comparable to that observed upon exposure to H2(18)O. The results of this investigation suggest that reoxidation of Mo(IV) cations following H2 reduction involves the formation of a Mo-peroxide species and subsequent O atom migration from such a species to the SiO2 support. It is proposed that the steady-state oxidation of H2 also involves the formation of Mo-peroxide species by interaction of O2 with a small number of Mo(IV) centers. The Mo-peroxide species are then rapidly reduced by H2 to form H2O and a Mo=O bond. The rapid exchange of O atoms between the gas phase and the catalyst observed during steady-state oxidation of H2 is attributed to interactions of the product H2O with the catalyst, rather than to O atom migration originating from the Mo-peroxide species formed on the catalyst surface.     

The generation and photochemistry of indenone o-oxide and fluorenone o-oxide in low temperature matrices

The photolysis of diazoindene and diazofluorene at 12K in N₂ matrices containing O₂ has been studied, using i.r. spectroscopy. The carbonyl oxides, indenone $\text{O}$-oxide and fluorenone $\text{O}$-oxide, were formed by the reaction of O₂ with the corresponding carbenes, and under appropriate conditions could be detected as very photolabile species. Photolysis of indenone $\text{O}$-oxide gave indenone and isocoumarin; similar photolysis of fluorenone $\text{O}$-oxide gave fluorenone and dibenzopyran-6-one.     

Targeted and modular architectural polymers employing bioorthogonal chemistry for quantitative therapeutic delivery

There remain several key challenges to existing therapeutic systems for cancer therapy, such as quantitatively determining the true, tissue-specific drug release profile in vivo, as well as reducing side-effects for an increased standard of care. Hence, it is crucial to engineer new materials that allow for a better understanding of the in vivo pharmacokinetic/pharmacodynamic behaviours of therapeutics. We have expanded on recent “click-to-release” bioorthogonal pro-drug activation of antibody-drug conjugates (ADCs) to develop a modular and controlled theranostic system for quantitatively assessing site-specific drug activation and deposition from a nanocarrier molecule, by employing defined chemistries. The exploitation of quantitative imaging using positron emission tomography (PET) together with pre-targeted bioorthogonal chemistries in our system provided an effective means to assess in real-time the exact amount of active drug administered at precise sites in the animal; our methodology introduces flexibility in both the targeting and therapeutic components that is specific to nanomedicines and offers unique advantages over other technologies. In this approach, the in vivo click reaction facilitates pro-drug activation as well as provides a quantitative means to investigate the dynamic behaviour of the therapeutic agent.

There remain several key challenges to existing therapeutic systems for cancer therapy, such as quantitatively determining the true, tissue-specific drug release profile in vivo, as well as reducing side-effects for an increased standard of care.     

Dichlorosilylene: Rate constant for reaction with carbon monoxide and nitrous oxide

The absolute rate constanss for the gas-phase reactions of 1,1-dichlorosilylene with carbon monoxide and nitrous oxide have been determined using the flash photolysts-kinetic absorpiton spectroscopy technique. The bimolecular rate constant values at 25° C are: $$\begin{gathered} k\left( {Cl_2 Si + CO} \right) = \left( {6.3 \pm 0.7} \right) \times 10^8 M^{ - 1} s^{ - 1} \hfill \\ k\left( {Cl_2 Si + N_2 O} \right) = \left( {5.7 \pm 0.3} \right) \times 10^8 M^{ - 1} s^{ - 1} \hfill \\ \end{gathered} $$      

Effects of ionizing radiation on linear aromatic polyesters

The influence of chemical structure on the response of aromatic polyesters to high-energy ionizing radiation was studied. Systematic variations of polymers related to poly(ethylene terephthalate) were subjected to γ radiation, and the competitive chain scission and crosslinking reactions were determined by measuring changes in intrinsic viscosity and molecular weights. It was found that an increase in the paraffinic glycol segment of polyterephthalates facilitated crosslinking, while the protective nature of aromatic groups was demonstrated by modifying the dibasic acid segments. The influence of substituents on the terephthalate moiety was mixed: electronegative groups led to chain scission (as evidenced by decreased viscosities), but electropositive substituents exerted a stabilizing effect on polymer viscosity. In almost all cases, number-average molecular weights were decreased by exposure to γ radiation, regardless of viscosity behavior. Crystalline melting temperatures of the polymers generally were decreased by the combined radiation effects of chain scission and crosslinking.     

The thermal decomposition of group iib metal halide complexes: Part II. N,N,N′,N′-tetramethylethylenediamine and 1,2-diphenylphosphinoethane complexes

The preparation and pyrolysis procedures for 1/1 complexes MX₂·L (where M = Group IIB metal, XCl, Br or I and LN,N,N′,N′-tetramethylethylene-diamine (TMED) or 1,2-diphenylphosphinoethane (DPE))is reported. The decomposition of the cadmium chloride and bromide TMED complexes afford intermediates of varying stability. From far infrared spectrophotometry we conclude that the chloride intermediate is a four coordinate polymeric complex. Differential scanning calorimetry has been used to determine selected latent heats of fusion.     

The effect of frequency on the plasma polymerization of ethane

The plasma polymerization of ethane has been studied in the frequency range of from 50 Hz to 13.56 MHz. The rate of polymer deposition is strongly dependent on frequency, with significantly higher rates being observed at frequencies below 6 MHz. The effects of frequency can be interpreted in terms of a mechanism that assumes that polymer is formed by the reaction of surface free radicals, created by the bombardment of the growing polymer by charged species, with gas phase free radicals, formed by collisions of energetic electrons with monomer molecules.     

Dianion metallation reactions of n,n-dimethylvanillylamine and n,n-dimethylisovanillylamine

The utility of dianion chemistry in the synthesis of polyfunctional aromatics is demonstrated by the direct lithiation of the vanillylamine 1 and by the metal-halogen exchange reaction of the bromo isovanillylamines 9 and 10.