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761.
Gagnepain J Moulin E Fürstner A 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(25):6964-6972
Iejimalide B ( 2 ) is the most promising member of a small family of marine polyene macrolides endowed with remarkably selective activity against human cancer cell lines. As this product, however, is hardly available from the natural sources, a detailed evaluation requires the development of an efficient and practical synthetic approach. This challenge has now been met by adapting the first total synthesis of 2 previously reported by our group to the needs of high material throughput. Redesigning the access routes to the five required building blocks in combination with a careful optimization of the fragment coupling processes provided gram amounts of this valuable compound in a sequence of no more than 16 linear steps with an overall yield of about 7 %. Key elements of the successful strategy include: i) three hydrostannylation processes of elaborate terminal alkynes with “lower order” stannyl cuprates, ii) a Brown allylation, a Noyori transfer hydrogenation, and a Marshall propargylation to set the chiral centers at C9, C17, C22 and C23, and iii) a modified Takai–Utimoto olefination for the preparation of the very labile skipped 1,4‐diene flanking the ester group. The assembly process benefited from a particularly mild protocol for the Stille cross‐coupling previously developed in this laboratory, which clearly outperformed the alternative Suzuki reaction in terms of yield and scalability. The 24‐membered macrocyclic frame was forged by a remarkably selective ring‐closing metathesis reaction (RCM), in which two out of the ten double bonds present in the cyclization precursor were selectively activated with the aid of a second‐generation Grubbs catalyst. 相似文献
762.
A computer simulation study of imaging flexural inhomogeneities using plate-wave diffraction tomography 总被引:2,自引:0,他引:2
This paper investigates the feasibility of plate-wave diffraction tomography for the reconstruction of flexural inhomogeneities in plates using the results of computer simulation studies. The numerical implementation of the fundamental reconstruction algorithm, which has recently been developed by Wang and Rose [C.H. Wang, L.R.F. Rose, Plate-wave diffraction tomography for structural health monitoring, Rev. Quant. Nondestr. Eval. 22 (2003) 1615-1622] is investigated addressing the essential effects of applying the discrete form of the Fourier diffraction theorem for solving the inverse problem as discussed by Kak and Slaney [A.C. Kak, M. Slaney, Principles of Computerized Tomographic Imaging, IEEE Press, New York, 1988] for the acoustic case, viz. diffraction limited sensitivity, influence of weak scatterer assumption, damage location and scatter field data processing in time and Fourier space as well as experimental limitations such as finite receiver length and limited views. The feasibility of the imaging technique is investigated for cylindrical inhomogeneities of various severities and relative position within the interrogation space and a normal incident interrogation configuration. The results show that plate-wave diffraction tomography enables the quantitative reconstruction of location, size and severity of plate damage with excellent sensitivity and offers the potential for detecting corrosion thinning, disbonds and delamination damage in structural integrity management applications. 相似文献
763.
Würger A 《Physical review letters》2008,101(10):108302
We study the thermal diffusion coefficient D{T} of a charged colloid in a temperature gradient, and find that it is to a large extent determined by the thermoelectric response of the electrolyte solution. The thermally induced salinity gradient leads in general to a strong increase with temperature. The difference of the heat of transport of coions and counterions gives rise to a thermoelectric field that drives the colloid to the cold or to the warm, depending on the sign of its charge. Our results provide an explanation for recent experimental findings on thermophoresis in colloidal suspensions. 相似文献
764.
Despina Charalambous Nicolas-George Homer Eliades Michalis Christoforou Eleni Kakouri Charalabos Kanakis Petros A. Tarantilis Maria Pantelidou 《Molecules (Basel, Switzerland)》2022,27(9)
This study aimed to determine the chemical composition of different types of tissue of Cedrus brevifolia Henry (Pinaceae) methanolic extracts, namely needles, twigs, branches, and bark. Cedrus brevifolia is a narrow endemic coniferous tree species of Cyprus, growing in a sole population in the mountainous area of Paphos Forest. Chemical analysis of the extracts was performed using liquid chromatography combined with time-of-flight high-resolution mass spectrometry (LC/Q-TOF/HRMS). The majority of the 36 compounds tentatively identified belonged to the flavonoids family. The extract of needles was the richest extract in terms of secondary metabolites. The extracts were studied for their antioxidant activity using the DPPH free radical scavenging assay. Additionally, the antibacterial activity was evaluated by determining both the minimum inhibitory concentration and the minimum bactericidal concentration against Staphylococcus aureus and Escherichia coli. All extracts demonstrated antioxidant property, while bark gave the highest antioxidant capacity (IC50 value of 0.011 mg/mL) compared to the other tissues. Antibacterial activity was observed against both types of bacteria, with the extract of branches presenting the strongest activity against S. aureus (MIC, 0.097 mg/mL and MBC, 0.195 mg/mL). This is the first time that extracts of needles, twigs, branches, and bark of C. brevifolia are compared regarding their chemical composition as well as their antimicrobial and antioxidant properties. 相似文献
765.
First, we simulate the behaviour of a satellite tethered with a continuous electrodynamic cable moving on a circular orbit. Second we extinguish for a simple discrete model small angle librations by controlling the current in the tether. (© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
766.
Matthias Peeters Dr. Jonathan Decaens Prof. Alois Fürstner 《Angewandte Chemie (International ed. in English)》2023,62(44):e202311598
Although 2-furyl-carbenes (furfurylidenes) are prone to instantaneous electrocyclic ring opening, chiral [BiRh]-paddlewheel complexes empowered by London dispersion allow (trifluoromethyl)furfurylidene metal complexes to be generated from a bench-stable triftosylhydrazone precursor. These reactive intermediates engage in asymmetric [2+1] cycloadditions and hence open entry into valuable trifluoromethylated cyclopropane or -cyclopropene derivatives in optically active form, which are important building blocks for medicinal chemistry but difficult to make otherwise. 相似文献
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