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101.
A simple, novel diastereoselective synthesis of both (E)- and (Z)-allylsilanes via organoboranes is developed. (E)-1-Alkenylboronate esters easily prepared from the corresponding terminal alkynes via hydroboration with dibromoborane-methyl sulfide complex followed by treatment with 1,3-propane diol readily react with trimethylsilylmethyllithium at −78 °C in methanol followed by reaction with iodine in methanol to produce the corresponding (Z)-allylsilanes in high yields (72-80%) and in high stereochemical purities (98% as evidenced by CMR spectral data). Similarly, the (Z)-1-alkenylboronate esters react with trimethylsilylmethyllithium at −78 °C in methanol followed by treatment with iodine in methanol to produce the corresponding (E)-allylsilanes in moderate yields (57-65%) in high stereochemical purities (>98% as revealed by CMR spectral data). 相似文献
102.
Paul W.R. Harris Victoria J. Muir Michelle Y.H. Lai Nicholas S. Trotter David J. Callis 《Tetrahedron》2005,61(42):10018-10035
The synthesis of ten proline-modified analogues of the neuroprotective tripeptide GPE is described. Five of the analogues incorporate a proline residue with a hydrophobic group at C-2 and two further analogues have this side chain locked into a spirolactam ring system. The pyrrolidine ring was also modified by replacing the γ-CH2 group with sulfur and/or incorporation of two methyl groups at C-5. 相似文献
103.
Levels of DNA strand breaks and DNA-protein cross-links (DPCs) were measured using the alkaline elution assay in normal human skin fibroblasts irradiated with 0-200 J m-2 of 254 nm UV radiation and incubated for 0-24 h. On incubation, the yields of both single-strand breaks (SSBs) and DPCs increased with similar kinetics and remained elevated. In addition, when SSBs were measured under conditions in which DPCs were not eliminated by treatment with proteinase K, a measurable yield of SSBs could not be detected. Hence, the SSBs that form in the UV-irradiated cells following incubation appear to be associated with the DPCs. 相似文献
104.
105.
[reactions: see text] [(Ph3P)CuH]6 effectively catalyzes the hydrostannation of activated alkynes with exclusive regioselectivity for alpha-stannation. Syn hydrostannation is observed exclusively for alkynoates. Anti or syn hydrostannation adducts are obtained as products for alkynone substrates. 相似文献
106.
Huang WL Cui SH Liang KM Gu SR Yuan ZF 《Journal of colloid and interface science》2002,246(1):129-134
Silica xerogels were prepared by thermal drying wet gels in an electric oven (70 degrees C) after certain duration of ambient drying, and the relevant effect is investigated on the mesopore structures and surface fractal dimensions of the resultant xerogels. The silica gels were derived from a hydrochloric acid-catalyzed TEOS (tetraethylorthaosilicate) system, and both magnetic stirring and ultrasonic vibration were adopted during sol preparation. The percentage mesoporosity and surface fractal dimensions are evaluated using image analysis methods, based on FE-SEM (field emission gun-scanning electron microscopy) images. The results show that the mesoporosity of the resultant xerogels decreases with the duration of ambient drying for samples prepared using magnetic stirring and low-intensity ultrasonic vibration, while samples subjected to high-intensity ultrasound show a somewhat reverse trend. Samples prepared with magnetic stirring have almost constant surface fractal dimensions (nearly 3), irrespective of the ambient drying before thermal drying. The surface fractal dimensions of samples prepared using ultrasound increase with the duration of ambient drying. 相似文献
107.
Yi-Chun Lai 《Tetrahedron》2005,61(40):9484-9489
Palladium-catalyzed Suzuki cross-coupling reactions employing Schiff-bases as ligands toward a series of substituted arylbromides and boronic acids were pursued. In the presence of a N,O-bidentate ligand, 2-[1-(2,4,6-trimethyl-phenylimino)-ethyl]-phenol 5, the catalytic reactions could be carried out efficiently at room temperature with a wide array of arylbromides, even with electronically deactivated arenes. A deprotonated 5, 5′, chelated palladium acetate complex, [5′Pd(II)(OAc)(solv)] 8, was proposed as a precursor of a genuine catalytically active species. 相似文献
108.
Matthew N. Idso Ajay Suresh Akhade Mario L. Arrieta-Ortiz Bert T. Lai Vivek Srinivas James P. Hopkins Jr. Ana Oliveira Gomes Naeha Subramanian Nitin Baliga James R. Heath 《Chemical science》2020,11(11):3054
Antibiotic resistant infections are projected to cause over 10 million deaths by 2050, yet the development of new antibiotics has slowed. This points to an urgent need for methodologies for the rapid development of antibiotics against emerging drug resistant pathogens. We report on a generalizable combined computational and synthetic approach, called antibody-recruiting protein-catalyzed capture agents (AR-PCCs), to address this challenge. We applied the combinatorial protein catalyzed capture agent (PCC) technology to identify macrocyclic peptide ligands against highly conserved surface protein epitopes of carbapenem-resistant Klebsiella pneumoniae, an opportunistic Gram-negative pathogen with drug resistant strains. Multi-omic data combined with bioinformatic analyses identified epitopes of the highly expressed MrkA surface protein of K. pneumoniae for targeting in PCC screens. The top-performing ligand exhibited high-affinity (EC50 ∼50 nM) to full-length MrkA, and selectively bound to MrkA-expressing K. pneumoniae, but not to other pathogenic bacterial species. AR-PCCs that bear a hapten moiety promoted antibody recruitment to K. pneumoniae, leading to enhanced phagocytosis and phagocytic killing by macrophages. The rapid development of this highly targeted antibiotic implies that the integrated computational and synthetic toolkit described here can be used for the accelerated production of antibiotics against drug resistant bacteria.Antibody-recruiting protein-catalyzed capture agent (AR-PCCs) are a new class of all-synthetic and highly targeted antibiotics that recruit endogenous immune responses to eliminate drug-resistant microbes. 相似文献
109.
Forty one terpenoidal compounds were isolated from the essential oil of Chamaecyparis formosensis Matsum. The dominant component is α-pinene. Other major components include β-pinene, 3-carene, α-terpineol, γ-muurolene, and kaurene. 相似文献
110.
The uranyl chelate of ferron was investigated polarographically over the pH range 1.98–10.00 and ligand concentration 0.005–0.060.M. A reversible and diffusion controlled reduction wave was obtained, however, when ferron concentration below 0.02M and pH below 5.0, it became irreversible. The chelate species identified were UO2(HA) 2 at pH range 2.5–7.1 and UO2(OH) (A) 2?3 over pH 7.1. The electron-transfer coefficient, rate constant, diffusion coefficient and activation energy of the reduction process were determined. 相似文献