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1.
Water is an efficient solvent for the Rh2(OAc)4 catalysed intramolecular C-H insertion of a range of diazo substrates without competitive water insertion. Due to the high solubility and stability of the catalyst in water, the catalyst can be efficiently reused. 相似文献
2.
Abstract— The 248 nm laser flash photolysis of myoglobin in various redox states (oxy, met and ferryl) in neutral aqueous solution yielded hydrated electrons with concurrent changes in the visible absorption spectrum of the heme. The results could be ascribed to the photoionization of both the peptide and the heme group, in approximately equal yields. The ionization of met- and ferrylmyoglobin was biphotonic, but that of oxymyoglobin was a mixture of mono- and biphotonic processes. Using appropriate electron and radical scavengers, the changes in the heme absorption could be investigated at times ≥100 ns and were shown to be associated with a +1 increase of the formal oxidation state of the heme. Using this method, the formal iron(V) state of native myoglobin could be spectroscopically characterized for the first time. Its absorption, blue-shifted and less intense relative to the ferryl state, is reminiscent of that of the compound I of peroxidases, which contains a ferryl-oxo (iron[IV]) group and a porphyrin radical cation. On this basis, the same structure is proposed for the formal iron(V) state of native myoglobin. The transition from oxy- to metmyoglo-bin took -5 μs, which may reflect the kinetics of exchange of oxygen with water as ligand. The transitions from the met to the ferryl state, and from ferryl to iron(V) states were faster (∽250 ns), consistent with processes that involve proton or electron movements but no changes in the iron coordination state. 相似文献
3.
The reaction of *OH with 2'-deoxyguanosine yields two transient species, both identified as OH adducts (G*-OH), with strongly different reactivity towards O2, or other oxidants, or to reductants. One of these, identified as the OH adduct at the C-8 position (yield 17% relative to *OH), reacts with oxygen with k=4 x 10(9)M(-1)s(-1); in the absence of oxygen it undergoes a rapid ring-opening reaction (k = 2 x 10(5) s(-1) at pH4-9), visible as an increase of absorbance at 300-310 nm. This OH adduct and its ring-opened successor are one-electron reductants towards, for example, methylviologen or [Fe(III)(CN)6]3-. The second adduct, identified as the OH adduct at the 4-position (yield of 60-70% relative to *OH), has oxidizing properties (towards N,N,N',N'-tetra-methyl-p-phenylenediamine, promethazine, or [Fe(II)(CN)6]4-). This OH adduct undergoes a slower transformation reaction (k = 6 x 10(3) s(-1) in neutral, unbuffered solution) to produce the even more strongly oxidizing (deprotonated, depending on pH) 2'-deoxyguanosine radical cation, and it practically does not react with oxygen (k< or = 10(6)M(-1)s(-1)). The (deprotonated) radical cation, in dilute aqueous solution, does not give rise to 8-oxoguanosine as a product. However, it is able to react with ribose with k< or =4 x 10(3)M(-1)S(-1). 相似文献
4.
Intramolecular C-H insertion using NHC-di-rhodium(II) complexes: the influence of axial coordination
In this work we show that the intramolecular C-H insertion of diazo-acetamides catalysed by di-rhodium(II) complexes can be highly influenced by the axial ligand on the di-rhodium(II) complex. Axially monocoordinated NHC-Rh2(OAc)4 complexes have a distinct reactivity from the parent Rh2(OAc)4 complex affording the cyclisation products in different rates and selectivities. Surprisingly, a new reaction mode emerged when using these complexes which led to a decarbonylation pathway. 相似文献
5.
A novel organocatalytic asymmetric [3+2] cycloaddition reaction between methyleneindolinones and allylic compounds yielding complex spirocyclopentaneoxindoles has been developed. It provides extraordinary levels of enantioselective control involving a chiral phosphine as a nucleophilic organocatalyst. Simple precursors were used under mild conditions to construct oxindole derivatives with high enantiopurity and structural diversity. This method should be useful in medicinal chemistry and diversity-oriented syntheses of these intriguing compounds. 相似文献
6.
Montalbano F Candeias NR Veiros LF André V Duarte MT Bronze MR Moreira R Gois PM 《Organic letters》2012,14(4):988-991
The dative N-B bond was used to simply assemble heterocycles with a skeleton akin to the 5-oxofuro[2,3-b]furan motif. Twenty-five new N-B heterocycles were prepared via a highly efficient one-pot four-component reaction in yields and diastereoselectivities up to 95% and >97%, respectively. Several reaction intermediates were discovered using electrospray ionization mass spectroscopy which set the basis for the mechanism elucidation using DFT calculations. 相似文献
7.
8.
M. Gil M.L. Carvalho A. Seruya I. Ribeiro I. Queralt A.E. Candeias J. Mirão 《Applied Physics A: Materials Science & Processing》2008,90(1):49-54
Pigments used in traditional limewashing paintings in Alentejo urban Heritage are inorganic materials and can be grouped into
four categories: a) reds – red ochre (from terras rossas, red schists and iron ore deposits weathering), almagres, terra roxa
(natural processed red ochres) and synthetic red iron oxides; b) yellows – yellow ochre (from schists and iron ore deposits),
processed natural ochres, yellow iron synthetic oxides, c) blacks – black earths and black iron synthetic oxides and d) blues
– artificial ultramarine. The present work proposes to characterize natural, natural processed and synthetic pigments by comparing
phase and elemental compositions. The results reveal differences in Fe, Si, K and Al total content according to their origin
and fabrication process and reveal intentional addition of white charges like carbonates. Elements like Zr, Ti, Cr, Mn, Ca
and Zn are present in all categories. Under optical microscopy, some samples of processed natural pigments do not exhibit
optical activity, thus revealing mixtures with synthetic pigments, while natural pigments present a strong birefringence colorless
due to optically active minerals.
PACS 78.70.En; 07.60.Pb; 61.10.Nz; 81.70.-q; 91.60.-x 相似文献
9.
Water is a suitable medium for the Petasis-borono-Mannich multicomponent reaction. Salicylaldehyde, glyoxalic acid, glycoaldehyde and glyoxal were reacted with several boronic acids and different amines affording alkylaminophenols, 2H-chromenes, α-amino acids, α-amino alcohols and 2-hydroxylmorpholines in good to high yields. An efficient new one-pot method for the assembly of boron-heterocycles based on amino-acids, boronic acids and salicylaldehyde using water as the reaction media is presented. The mechanisms of these reactions were studied by means of DFT calculations, and the effect of solvent on the calculated energy barriers was addressed, for different aldehydes. 相似文献
10.
Preferential Rh(II) carbenoid intramolecular C-H versus O-H insertion derived from alpha-diazo-acetamides can be achieved in water by using an appropriate combination of the catalyst and amide groups, which creates a larger hydrophobic environment around the reactive carbenoid center. 相似文献