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1.
Iodine(III)‐Catalyzed Rearrangements of Imides: A Versatile Route to α,α‐Dialkylated α‐Hydroxy Carboxylamides
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Anna Ulmer Dr. Maciej Stodulski Stefanie V. Kohlhepp Christoph Patzelt Dr. Alexander Pöthig Dr. Wolfgang Bettray Dr. Tanja Gulder 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(4):1444-1448
A tertiary hydroxy group α to a carboxyl moiety comprises a key structural motif in many bioactive substances. With the herein presented metal‐free rearrangement of imides triggered by hypervalent λ3‐iodane, an easy and selective way to gain access to such a compound class, namely α,α‐disubstituted‐α‐hydroxy carboxylamides, was established. Their additional methylene bromide side chain constitutes a useful handle for rapid diversification, as demonstrated by a series of further functionalizations. Moreover, the in situ formation of an iodine(III) species under the reaction conditions was proven. Our findings clearly corroborate that hypervalent λ3‐benziodoxolones are involved in these organocatalytic reactions. 相似文献
2.
We give an overview of current methods for the detection of point mutations as well as small insertions and deletions in clinical diagnostics. For each method, the following characteristics are specified: (a) principle, (b) major modifications, (c) maximum fragment size that can be analyzed, (d) ratio and type of mutations that can be detected (e) minimum ratio of mutant to wild-type alleles at which mutations can be detected, and (j) detection methods. Special attention is paid to the possibilities of quality assessment and the potential for standardization and automation. 相似文献
3.
Slootweg JC Vlaar MJ Vugts DJ Eichelsheim T Merhai W de Kanter FJ Schakel M Ehlers AW Lutz M Spek AL Lammertsma K 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(16):4808-4818
Reaction of the transient phosphinidene complexes R-P=W(CO)5 with N-substituted-diphenylketenimines leads unexpectedly to the novel 2-aminophosphindoles, as confirmed by an X-ray crystal structure determined for one of the derivatives. Experimental evidence for a methylene-azaphosphirane intermediate was found by using the iron-complexed phosphinidene iPr2N-P=Fe(CO)4, which affords the 2-aminophosphindole together with the novel methylene-2,3-dihydro-1H-benzo[1,3]azaphosphole. Analysis of the reaction pathways with DFT indicates that the initially formed methylene-azaphosphirane yields both phosphorus heterocycles by way of a [1,5]- or [1,3]-sigmatropic shift, respectively, followed by a H-shift. Strain underlies both rearrangements, which causes these remarkably selective conversions that can be tuned by changing the substituents. 相似文献
4.
The stepwise addition polymerization reactions of bisazlactones [bis(2-oxazolin-5-one)s] and a variety of 4,4′-bisphenols have been studied for the purpose of making thermally reversible linear polymers. Thus polymerization occurs at or near room temperature, while depolymerization yielding the two monomer species occurs at elevated temperatures. The synthesis of oligomers in solution without the use of catalyst occurs for the reaction of bisazlactones with bisphenols containing an electron-withdrawing moiety between the two phenol groups of the bisphenol. These oligomers regenerate the bisphenol and bisazlactone monomers upon heating to 165–200°C for several hours under dry box conditions. In many cases, these reactions follow the same patterns of reactivity observed in model studies. This chemistry may be useful for forming degradable or recyclable polymers, where shortchain prepolymers, or macromonomers, endcapped with azlactone and phenol moieties could be used to form high molecular weight polymers that are thermoreversible. Such a reaction system might also be used for preventing reactions of bisphenols and/or bisazlactones at low temperatures, with the desired reaction initiated by formation of the reactive species at elevated temperatures. Envisioned uses in this case might be thermally triggered crosslinking or polymerization reactions, or temperature controlled drug release. © 1993 John Wiley & Sons, Inc. 相似文献
5.
Conformational stability of G-quartets found in telomeric DNA quadruplex structures requires the coordination of monovalent ions. Here, an extensive Hartree-Fock and density functional theory analysis of the energetically favored position of Li+, Na+, and K+ ions is presented. The calculations show that at quartet-quartet distances observed in DNA quadruplex structures (3.3 A), the Li+ and Na+ ions favor positions of 0.55 and 0.95 A outside the plane of the G-quartet, respectively. The larger K+ ion prefers a central position between successive G-quartets. The energy barrier separating the minima in the quartet-ion-quartet model are much smaller for the Li+ and Na+ ions compared with the K+ ion; this suggests that K+ ions will not move as freely through the central channel of the DNA quadruplex. Spin-spin coupling constants and isotropic chemical shifts in G-quartets extracted from crystal structures of K+- and Na+-coordinated DNA quadruplexes were calculated with B3LYP/6-311G(d). The results show that the sizes of the trans-hydrogen-bond couplings are influenced primarily by the hydrogen bond geometry and only slightly by the presence of the ion. The calculations show that the R(N2N7) distance of the N2-H2...N7 hydrogen bond is characterized by strong correlations to both the chemical shifts of the donor group atoms and the (h2)J(N2N7) couplings. In contrast, weaker correlations between the (h3)J(N1C6') couplings and single geometric factors related to the N1-H1...O6=C6 hydrogen bond are observed. As such, deriving geometric information on the hydrogen bond through the use of trans-hydrogen-bond couplings and chemical shifts is more complex for the N1-H1...O6=C6 hydrogen bond than for the N2-H2...N7 moiety. The computed trans-hydrogen-bond couplings are shown to correlate with the experimentally determined couplings. However, the experimental values do not show such strong geometric dependencies. 相似文献
6.
The biochemical transport and binding of nicotine depends on the hydrogen bonding between water and binding site residues to the pyridine ring and the protonated pyrrolidinium ring. To test the independence of these two moderately separated hydrogen-bonding sites, we have calculated the structures of clusters of protonated nicotine with water and a bicarbonate anion, benzene, indole, or a second water molecule. Unprotonated nicotine-water clusters have also been studied for contrast. The potential energy surfaces are first explored with an intermolecular anisotropic atom-atom model potential. Full geometry optimizations are then carried out using density functional theory to include nonadditive terms in the interaction energies. The presence of the charge on the pyrrolidine nitrogen removes the conventional hydrogen-bonding site on the pyridine ring. The hydrogen-bond ability of this site is nearly recovered when the protonated pyrrolidinium ring is bound to a bicarbonate anion, whereas its interaction with benzene shows a much smaller effect. Indole appears to partially restore the hydrogen-bond ability of the pyridine nitrogen, although indole and benzene both pi-bond to the pyrrolidinium ring. A second hydrogen-bonding water produces a significant conformational distortion of the nicotine. This demonstrates the limitations of the conventional qualitative predictions of hydrogen bonding based on the independence of molecular fragments. It also provides benchmarks for the development of atomistic modeling of biochemical systems. 相似文献
7.
Two pyrene-labeled hydroxylamines, 5-Bn and 5-Bz, O-protected with the benzyl and the benzoyl group, respectively, have been prepared for the generation of siderophore-based new chelators incorporating both the pyrene chromophore and the hydroxamic acid functionality. 5-Bz formed the starting point toward the synthesis of the tripod-shaped trishydroxamate, 1. That trichromophoric ligand displays remarkable fluorescence emission properties (dual emission: "monomer" and excimer type) which are markedly and selectively modified by binding Fe(NO(3))(3) and Ga(NO(3))(3). Ferric ions induce a quasi total quenching of the pyrene fluorescence, whereas the nonquenching Ga(III) cations are observed to affect the value of the excimer-to-monomer fluorescence intensity ratio. Ethylenediaminetetraacetic acid (EDTA) competition reactions yielded an estimated value of 3.8 for log K of the complex LFe in methanol/water (80/20 v/v), where K = ([LFe][H(+)](3))/([LH(3)][Fe(3+)]) and L is the ligand in its totally deprotonated form. Compound 1 is the prototype of a new class of photoresponsive molecular systems which could act as sensitive probes for metal cation detection and recognition. 相似文献
8.
Ingo Hartenbach Falk Lissner Tanja Nikelski Steffen F. Meier Helge Müller‐Bunz Thomas Schleid 《无机化学与普通化学杂志》2005,631(12):2377-2382
About Lanthanide Oxotantalates with the Formula MTaO4 (M = La – Nd, Sm – Lu) Besides being a by‐product of solid state syntheses in tantalum ampoules the lanthanide(III) oxotantalates of the formula MTaO4 can be easily prepared by sintering lanthanide sesquioxide M2O3 and tantalum(V) oxide Ta2O5 with sodium chloride as flux. Under these conditions two structure types emerge depending upon the M3+ cationic radius. For M = La – Pr the MTaO4‐type tantalates crystallize in the space group P21/c with lattice constants of a = 762(±1), b = 553(±4), c = 777(±4) pm, β = 101(±1)° and four formula units per unit cell. With M = Nd, Sm – Lu, the monoclinic cell dimensions (space group P2/c) shrink to the lattice constants like a = 516(±9), b = 551(±9), c = 534(±9) pm, β = 96.5(±0.3)° and there are only two formula units present. Both structures show a coordination sphere of eight oxygen atoms for the lanthanide trications shaped as distorted square antiprism for the structure with the larger lanthanides (in the following referred to as A‐type) and as trigonal dodecahedron for the structure with the smaller ones (called as B‐type in the following). The coordination environment about the Ta5+ cations can be described as a slightly distorted octahedron (CN = 6) for the A‐type structure of MTaO4 and a heavily distorted one (CN = 6) for the B‐type. The difference between the two types results from the interconnection of these [TaO6]7? octahedra. Whereas they are connected via four vertices to form corrugated layers according to parallel the bc‐plane in the A‐type, the octahedra of the B‐type MTaO4 structure share edges to built up zig‐zag chains along the c axis. 相似文献
9.
The elucidation of metal ion binding mechanisms with chelating resins by treating the resin as a collection of monomeric units is an established approach. In this paper, this approach is used to treat data obtained from two-phase potentiometric titrations by the programme ESTA. Apparent protonation and formation constants could be calculated. From these, species distribution plots could be obtained. These, in turn, allowed the calculation of the more familiar distribution ratios. The method was tested on Fe(III) and Nd(III) bonding with the iminodiacetate functionalized resin, Chelex 100; and Ca(II) bonding to the aminomethylphosphonate functionalized resin, Purolite S940. Good results were obtained indicating the applicability of this method. Comparisons with the literature are made. 相似文献
10.