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31.
32.
Colin Eaborn Anna Kowalewska Wlodzimierz Stanczyk 《Journal of organometallic chemistry》1998,560(1-2)
The finding that compounds of the type (Me3Si)2(PhMe2Si)CSiMePhX react with electrophiles to give very predominantly rearranged products (Me3Si)2(Ph2MeSi)CSiMe2Y, which would be expected to be thermodynamically disfavoured, can be rationalized in terms of a mechanism in which the anchimerically-assisted departure of X− gives the Ph-bridged cation [(Me3Si)2
MePh]+ which is attacked by the nucleophile at the less hindered centre bearing two Me groups rather than that bearing one Me and one Ph group, with the outcome determined by kinetic rather than thermodynamic factors. Both (Me3Si)2(Ph2MeSi)CSiMe2Br and its isomer (Me3Si)2(PhMe2Si)CSiMePhBr react with AgBF4 in CH2Cl2 or Et2O to give >95% of the fluoride (Me3Si)2(Ph2MeSi)CSiMe2F. Reaction of the bromide (Me3Si)2(PhMe2Si)CSiMePhBr with AgO2CCF3 in Et2O, and that of the hydride (Me3Si)2(PhMe2Si)CSiMePhH with ICl in CCl4, likewise give >95% of the rearranged (Me3Si)2(Ph2MeSi)CSiMe2O2CCF3 and (Me3Si)2(Ph2MeSi)CSiMe2Cl, respectively. 相似文献
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33.
The thermal treatment of N-(2-propenyl)-1-naphthylamines provided the expected aza-Claisen rearranged products, 2-(2-propenyl)-1-naphthylamines and benz[g]indoles, these last derived from an intramolecular hydroamination reaction on those primary products. The 2-(2-propenyl)-1-naphthylamines were converted into their triphenylphosphazene derivatives, which by aza-Wittig reaction with disubstituted ketenes yielded N-[2-(2-propenyl)-1-naphthyl] ketenimines. The heating of these ketenimines in boiling toluene induced their cyclization either via an intramolecular Diels-Alder reaction, to afford dibenz[b,h]acridines, or via [1,5] hydrogen migration from the sp3 carbon atom of the propenyl substituent to the central carbon atom of the ketenimine fragment, followed by a 6π electrocyclic ring closure, to give benzo[h]quinolines. 相似文献
34.
《Tetrahedron letters》2005,46(16):2771-2774
Treatment of 3β-acetoxy-5-bromo-6β,19-epoxy-5α-androstan-17-one with Ac2O and BF3·OEt2, produced the cleavage of the epoxy moiety and migration of the bromine atom to afford 3β,19-diacetoxy-6α-bromo-5-hydroxy-5β-androst-17-one in high yield. 相似文献
35.
Chao Song Dan Gao Tianying Yuan Yongli Chen Liping Liu Xiaowu Chen Yuyang Jiang 《中国化学快报》2019,30(5):1038-1042
Cell migration and invasion are critical steps in cancer metastasis, which are the major cause of death in cancer patients. Tumor-associated macrophages(TAMs) and interstitial flow(IF) are two important biochemical and biomechanical cues in tumor microenvironment, play essential roles in tumor progression. However, their combined effects on tumor cell migration and invasion as well as molecular mechanism remains largely unknown. In this work, we developed a microfluidic-based 3 D breast cancer model by co-culturing tumor aggregates, macrophages, monocytes and endothelial cells within 3 D extracellular matrix in the presence of IF to study tumor cell migration and invasion. On the established platform, we can precisely control the parameters related to tumor microenvironment and observe cellular responses and interactions in real-time. When co-culture of U937 with human umbilical vein endothelial cells(HUVECs) or MDA-MB-231 cells and tri-culture of U937 with HUVECs and MDA-MB-231 cells, we found that mesenchymal-like MDA-MB-231 aggregates activated the monocytes to TAM-like phenotype macrophages. MDA-MB-231 cells and IF simultaneously enhanced the macrophages activation by the stimulation of colony-stimulating factor 1(CSF-1). The activated macrophages and IF further promoted vascular sprouting via vascular endothelial growth factor(VEGFα) signal and tumor cell invasion. This is the first attempt to study the interaction between macrophages and breast cancer cells under IF condition. Taken together, our results provide a new insight to reveal the important physiological and pathological processes of macrophages-tumor communication. Moreover, our established platform with a more mimetic 3 D breast cancer model has the potential for drug screening with more accurate results. 相似文献
36.
Six pentacyclic triterpene acids, ursolic acid, oleanolic acid, betulinic acid, 23-hydroxybetulinic acid, glycyrrhetinic acid, and senegenin, were metabolized by the microbe Nocardia sp. NRRL 5646 to selectively furnish their corresponding 28-methyl esters. Notably, ursolic acid (1) was converted to oleanolic acid methyl ester (4) via two intermediates, oleanolic acid (2), and ursolic acid methyl ester (3), which are formed by participation of ‘retro-biosynthetic’ methyl migration from C-19 to C-20. Senegenin (11) was selectively converted to a nortriterpene methyl ester, senegenic acid methyl ester (12), via an unprecedented C-C bond cleavage. The stereochemical assignments of compounds 11 and 12 were made unambiguously for the first time using 2D NMR spectroscopy. 相似文献
37.
用分子动力学方法模拟了金属铜纳米双晶中晶界在应变作用下的迁移过程,晶界类型为〈11l〉倾侧∑19晶界。原子问相互作用力采用Finnis-Sinclair型EAM势计算。结果表明:平行于晶界方向的压应变可以促进晶界在相邻品界交互作用下发生迁移;垂直于晶界方向的压应变则不能对晶界迁移产生明显的效果。晶界迁移大致可分为两个阶段,前阶段晶界迁移缓慢,随晶界间距减小,晶界间交互作用加强,使晶界迁移显著加速。 相似文献
38.
采用密度泛函理论B3LYP/6-31G(d,p)方法研究了2-(2-甲基丙烯基)-3-(3-甲基-1,2-丁二烯基)环己-2-烯酮重排生成八元环化合物在气相中的反应机理. 考虑了两条可能的反应途径: 途径1包含5个过程, 途径2包含两个过程. 从能量上看, 两条途径的决定速度步均是[1,5]氢迁移. 采用自洽反应场极化连续模型(PCM模型)和极化导体模型(CPCM模型)研究了反应体系在甲苯溶液中的溶剂效应. 结果表明, 气相和溶液中途径2均是较优途径, 并且甲苯对该反应的溶剂化效应不明显. 理论研究结果与实验观察结果一致, 并很好地解释了有关实验现象. 相似文献
39.
40.
应用改进分析型嵌入原子方法(MAEAM)计算fcc金属的结构稳定性和声子谱.考虑更远邻原子之间的相互作用,提出新的两体势函数,并采用新的截尾处理函数和加强光滑连接条件.通过拟合单空位迁移能、结合能、三个独立弹性常数及晶体平衡条件,确定了模型参数.在体积不变条件下,计算金属不同结构的能量,说明Ag、Al、Au、Cu、Ir、Ni、Pd、Pt和Rh的fcc结构比较稳定.它们的能量-体积曲线与Rose方程结果基本-致,进-步说明了体积变化时的结构稳定性.同时发现[100]、[110]和[111]三个方向声子谱的计算结果符合实验值和其它计算结果. 相似文献