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261.
Rao Kolluri Jing Zhang Rajinder Singh Matthew A.J. Duncton 《Tetrahedron letters》2018,59(47):4158-4160
Attempted cyclization of (4-(hydroxymethyl)-8-nitro-4H-benzo[b]tetrazolo[1,5-d][1,4]oxazin-4-yl)methyl 4-methylbenzenesulfonate 2 did not give the expected spirooxetane product 1, but instead provided 9-nitro-5H-spiro[benzo[b]tetrazolo[1,5-d][1,4]oxazepine-4,2′-oxirane] 3via an unusual ring-expansion process. The structure of compound 3 was confirmed by single-crystal X-ray crystallography. The spiroepoxide (oxirane) in compound 3 could be ring-opened with a variety of nucleophiles to give products of potential interest to medicinal chemists. 相似文献
262.
The First total Synthesis of Brevipolide N and total Synthesis Brevipolide M have been accomplished from commercially available d-Mannitol. The key features of the syntheses are the use of Horner–Wadsworth–Emmons olefination, Noyori reduction, Acid catalyzed epoxide opening and Lindlars reaction. 相似文献
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264.
Mycobacterium tuberculosis (Mtb) is the causative organism of tuberculosis. Extensively drug resistant strains and latency have posed formidable challenges in the treatment of tuberculosis. The current study addresses an alpha/beta hydrolase fold bearing enzyme, epoxide hydrolase Rv1938 from Mtb. Epoxide hydrolases are involved in detoxification processes, catabolism and regulation of signaling molecules. Using GROMACS, a 100 ns Molecular Dynamics (MD) simulation was performed for Rv1938. Cavities were identified within the protein at various time frames of the simulation and their volumes were computed. During MD simulation, in addition to the substrate binding cavity, opening of two new cavities located behind the active site was observed. These cavities may be similar to the backdoor proposed for acetylcholinesterase. Structural superimposition of epoxide hydrolase from Mtb with the epoxide hydrolase of Agrobacterium radiobacter1 AD1 (Ephy) indicates that cavity1 in Mtb lies at an identical position to that of the water tunnel in Ephy. Further, docking of the substrate and an inhibitor with protein structures obtained from MD simulation at various time frames was also performed. The potential role of these cavities is discussed. 相似文献
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266.
Copolymerization is a commonly employed method for optimizing the properties of polymer materials. Incorporating ether segments into polyesters main chain to obtain polyether-polyester copolymers is an effective strategy to realize the integration of multiple properties of polyester and polyether, and to develop more high-performance, multi-purpose polymer materials. Herein, the synthesis of poly(ether-ester)s is accessible by employing the biphenyl-linked heterodinuclear salen Cr-Al complex in the presence of PPNCl for the copolymerization of epoxides and ε-caprolactone(CL). Monitoring the copolymerization process reveals that catalyst 1 exhibited good performance for the copolymerization of epoxides and CL, affording copolymers with a gradient sequence structure. The dynamic thermomechanical analysis(DMA) study indicates the obtained poly(ether-ester)s possess enhanced flexibility compared with the block copolymers or blend of PPO and PCL homopolymers with the same ratio. This study provides a theoretical basis for the preparation of high-performance polymer materials. 相似文献
267.
Polyethylene Glycol Functionalized Magnetic Dicationic Ionic Liquids as a Novel Catalyst and Their Application in Ring Opening of Epoxides in Water 下载免费PDF全文
A simple and environmentally benign protocol for the aqueous synthesis of 1,2‐azidoalcohols via regioselective ring opening of 1,2‐epoxides using PEG‐MDIL as a novel magnetic phase transfer catalyst is described. The catalyst was studied by UV spectroscopy, IR spectroscopy, and thermogravimetric analysis. The reactions occur in water and furnish the corresponding azidoalcoholes in high yields. No evidence for the formation of by‐product and the products were obtained in pure form without further purification. 相似文献
268.
Jia-Liang Yang Hai-Lin Wu Yang Li Prof. Xing-Hong Zhang Prof. Donald J. Darensbourg 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(21):5868-5873
The preparation of perfectly alternating and regioslective copolymers derived from the copolymerization of carbonyl sulfide (COS) and epoxides by metal-free Lewis pair catalysts composed of a Lewis base (amidine, guanidine, or quaternary onium salts) and a Lewis acid (triethyl borane) is described. Colorless and highly transparent copolymers of poly(monothiocarbonate) were successfully obtained with over 99 % tail-to-head content and high molecular weight (up to 92.5 kg mol−1). In most instances, oxygen–sulfur exchange reactions (O/S ERs), which would generate random thiocarbonate and carbonate units, were effectively suppressed. The turnover frequencies (TOF) of these Lewis pair catalyzed processes were as high as 119 h−1 at ambient temperature. 相似文献
269.
The ring opening reaction of epoxidized natural rubber (ENR-50) in the presence of potassium hydroxide/isopropanol solution was studied using NMR, and it's thermal characteristic was investigated using TG/DTG and DSC. 1H-NMR showed that 16.9% of epoxide units was ring-opened in treated ENR-50, which was also supported by quantitative FTIR spectroscopy. 13C-NMR proved the location of alkyl group (isopropyl) in the polymer chain of treated ENR-50. The attachment location of isopropyl occurred at both most (↑) and least (↓) hindered carbons of the epoxide. 2D-NMR was used to identify and scrutinize the triad assignment of treated ENR-50. The TG/DTG results presented three decomposition steps at 190-331, 331-521 and 521–706 °C due to the existence of mixtures of polymer chains i.e. ring-opened and intact epoxide of ENR-50, which also led to increase in Tg of treated ENR-50 at 13.2 °C compared with purified ENR-50 at −17.7 °C. 相似文献
270.
《Comptes Rendus Chimie》2014,17(5):450-453
A task-specific ionic liquid as an environmentally eco-friendly green catalyst has been synthesized and used in the ring opening of epoxides under green conditions. In order to use protic ionic liquids (PIL), we decided to synthesize 1,2-azidoalcohols via a ring opening reaction of epoxides with 1-hydrogen-3-methylimidazolium azide ([Hmim]N3), which actually acts as a solvent, a reagent and an activator of the epoxide ring. The reaction was carried out in short times (50–70 min) at 70 °C to give 1,2-azidoalcohol in 80–94% isolated yields. 相似文献