排序方式: 共有62条查询结果,搜索用时 15 毫秒
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Warren SA Stokes S Frampton CS White AJ Spivey AC 《Organic & biomolecular chemistry》2012,10(24):4685-4688
The first synthesis of hydroxy-iso-evoninic acid (2), a pyridyl diacid found as a macrodilactone bridging ligand in bioactive Celastraceae sesquiterpenoid-based natural products, has been achieved in 9 steps and an overall yield of 26%. The synthesis utilizes a benzilic ester rearrangement (BER) and a late stage benzylic oxidation to give access to all four stereoisomers whose absolute stereochemistry was assigned following chromatographic separation and anomalous dispersion X-ray crystallography. 相似文献
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Offermann DA McKendrick JE Sejberg JJ Mo B Holdom MD Helm BA Leatherbarrow RJ Beavil AJ Sutton BJ Spivey AC 《The Journal of organic chemistry》2012,77(7):3197-3214
The disruption of the human immunolobulin E-high affinity receptor I (IgE-FcεRI) protein-protein interaction (PPI) is a validated strategy for the development of anti asthma therapeutics. Here, we describe the synthesis of an array of conformationally constrained cyclic peptides based on an epitope of the A-B loop within the Cε3 domain of IgE. The peptides contain various tolan (i.e., 1,2-biarylethyne) amino acids and their fully and partially hydrogenated congeners as conformational constraints. Modest antagonist activity (IC(50) ~660 μM) is displayed by the peptide containing a 2,2'-tolan, which is the one predicted by molecular modeling to best mimic the conformation of the native A-B loop epitope in IgE. 相似文献
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Tzu-Chia Chen Mahyuddin KM Nasution Abdullah Hasan Jabbar Sarah Jawad Shoja Waluyo Adi Siswanto Sigiet Haryo Pranoto Dmitry Bokov Rustem Magizov Yasser Fakri Mustafa A. Surendar Rustem Zalilov Alexandr Sviderskiy Alla Vorobeva Dmitry Vorobyev and Ahmed Alkhayyat 《中国物理 B》2022,31(9):96401-096401
Understanding the relation between spatial heterogeneity and structural rejuvenation is one of the hottest topics in the field of metallic glasses (MGs). In this work, molecular dynamics (MD) simulation is implemented to discover the effects of initial spatial heterogeneity on the level of rejuvenation in the Ni$_{80}$P$_{20 }$MGs. For this purpose, the samples are prepared with cooling rates of $10^{10}$ K/s-$10^{12}$ K/s to make glassy alloys with different atomic configurations. Firstly, it is found that the increase in the cooling rate leads the Gaussian-type shear modulus distribution to widen, indicating the aggregations in both elastically soft and hard regions. After the primary evaluations, the elastostatic loading is also used to transform structural rejuvenation into the atomic configurations. The results indicate that the sample with intermediate structural heterogeneity prepared with 10$^{11}$ K/s exhibits the maximum structural rejuvenation which is due to the fact that the atomic configuration in an intermediate structure contains more potential sites for generating the maximum atomic rearrangement and loosely packed regions under an external excitation. The features of atomic rearrangement and structural changes under the rejuvenation process are discussed in detail. 相似文献
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Michael Z. Spivey 《Discrete Mathematics》2007,307(24):3130-3146
We present a new approach to evaluating combinatorial sums by using finite differences. Let and be sequences with the property that Δbk=ak for k?0. Let , and let . We derive expressions for gn in terms of hn and for hn in terms of gn. We then extend our approach to handle binomial sums of the form , , and , as well as sums involving unsigned and signed Stirling numbers of the first kind, and . For each type of sum we illustrate our methods by deriving an expression for the power sum, with ak=km, and the harmonic number sum, with ak=Hk=1+1/2+?+1/k. Then we generalize our approach to a class of numbers satisfying a particular type of recurrence relation. This class includes the binomial coefficients and the unsigned Stirling numbers of the first kind. 相似文献
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A new germanium-based linker for solid phase synthesis of aromatics: synthesis of a pyrazole library
An efficient synthesis of chlorogermane linker 12 is described. Economic introduction of germanium into this linker is accomplished by insertion of dichlorogermylene [from germanium(IV) chloride] into the homobenzylic C-Cl bond of 4-(2-chloroethyl)phenol 1. Using linker 12, transmetalation with lithiated 4-acetophenone, 3-acetophenone, and 4-(4'methoxy)biphenyl followed by Mitsunobu-type coupling to Argogel gives functionalized resins 14, 16, and 18, respectively. Treatment of resin 18 with TFA, ICl, Br2, or NCS effects clean ipso-degermylation releasing biphenyls 19-22, respectively. Resins 14 and 16 are employed for the parallel synthesis of a library of pyrazoles by enaminone formation (using Bredereck's reagent), condensative ring-closure (using a series of monosubstituted hydrazines), and cleavage (using TFA and Br2). Analysis of this library reveals the influence of the hydrazine substituent on both the regioselectivity of ring-closure and the propensity for electrophilic substitution at the 4-position of the pyrazoles during ipso-degermylative cleavage. 相似文献
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A host-guest optical sensor for the determination of aliphatic amines as exemplified by octylamine is proposed. It is based on the reversible fluorescence enhancement of heptakis(2,6-di-O-isobutyl)-β-cyclodextrin(DOB-β-CD) hosting tetraphenylporphyrin (TPP) immobilized in poly(vinyl chloride) (PVC) membrane by aliphatic amine extracted from aqueous phase into membrane phase. The optimum membrane contained 1.15 wt % TPP, 6.15 wt % DOB-β-CD as sensing reagent and other membrane materials. The fluorescence enhancement of the membrane resulted from the formation of a stable three-component complex among DOB-β-CD, TPP, and aliphatic amines. With the optimum conditions described, the fluorescence response of the sensor to octylamine shows a good correlation with the theoretically derived equation in the range 1.0 × 10–6 to 8.0 × 10–4 mol/L. The response characteristics including reversibility, response time, reproducibility and lifetime and selectivity of this optical device are also discussed in detail. This sensor has also been applied for the determination of octylamine in water samples containing interferents with satisfactory recovery. 相似文献
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meta-Selective C–H functionalisation of aryl boronic acids directed by a MIDA-derived boronate ester
Alexander F. Williams Andrew J. P. White Alan C. Spivey Christopher J. Cordier 《Chemical science》2020,11(12):3301
N-Methyliminodiacetic acid (MIDA) boronates are boronic acid derivatives which are stable to reduction, oxidation and transmetalation. This has led to their widespread use as boronic acid protecting groups (PGs) and in iterative cross-couplings. We describe herein the development of a novel MIDA derivative that acts in a dual manner, as a protecting group and a directing group (DG) for meta C(sp2)–H functionalisation of arylboronic acids. Palladium catalysed C–H alkenylations, acetoxylations and arylations are possible, at room temperature and under aerobic conditions. Deprotection to reveal the functionalised boronic acids is rapid and allows for full recovery of the DG. The technique allows the facile diversification of aryl boronic acids and their subsequent use in a range of reactions or in iterative processes.An N-methyliminodiacetic acid derivative allows the meta-C–H functionalisation of boronic acids, acting simultaneously as a directing and protecting group. 相似文献
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A C Spivey P Charbonneau T Fekner D H Hochmuth A Maddaford C Malardier-Jugroot A J Redgrave M A Whitehead 《The Journal of organic chemistry》2001,66(22):7394-7401
The barriers to enantiomerization of a series of axially chiral biaryl analogues of 4-(dimethylamino)pyridine (DMAP) 1-10 were determined experimentally by means of dynamic HPLC measurements and racemization studies. The barriers to rotation in derivatives 1-6 (based on the bicyclic 5-azaindoline core) were lower than those in the corresponding derivatives 7-10 (based on the monocyclic DMAP core). Semiempirical (PM3), ab initio Hartree-Fock (HF/STO-3G), and density functional theory (DFT/B3LYP/6-31G*) calculations reveal that these differences in barriers to rotation are the result of differing degrees of hybridization of the non-pyridyl nitrogen in the enantiomerization transition states (TSs). The importance of heteroatom hybridization as a factor in determining nonsteric contributions to barriers to rotation in azabiaryls of this type is discussed. 相似文献