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21.
Luc Martinon Stéphane Azoulay E. Peter Kündig 《Journal of organometallic chemistry》2004,689(23):3831-3836
A Pd-catalyzed three-component assembling of highly functionalized 4-benzyl-(and allyl-)pyrrolidines was achieved based on a combination of allyl amines, gem-diactivated alkenes, and unsaturated halides (or triflate). 相似文献
22.
The Mannich-type reaction of imines with (1-methoxy-2-methylpropenyloxy)trimethylsilane and aza-Diels-Alder reaction of imines with Danishefsky's diene can be carried out in scCO2 in the presence of lithium heptadecafluorooctanesulfonate which offer a way to synthesize β-amino carbonyl compounds and nitrogen-containing six-membered ring compounds under environmentally benign conditions. 相似文献
23.
Mingbao Zhang Raymond Reeves Cheng Bi Robert Dally Gaetan Ladouceur William Bullock Jefferson Chin 《Tetrahedron letters》2004,45(27):5229-5231
Three novel, optically active, 6-substituted 2-(aminomethyl)chromans were synthesized from readily available chroman 2-carboxylic acid precursors. These chroman-containing primary amines are useful building blocks for the synthesis of chroman-derived pharmaceutical agents. 相似文献
24.
Fukuji Higashi Kanako Sugishita 《Journal of polymer science. Part A, Polymer chemistry》2004,42(1):44-51
A two‐stage co‐oligomerization of the oligomers initially formed from an equimolar mixture of isophthalic acid (IPA) and terephthalic acid (TPA) and 2,2‐bis(4‐hydroxyphenyl)propane (BPA, 50 mol %) with bisphenols (BPs, 20 mol %) was carried out using a tosyl chloride/dimethylformamide/pyridine condensing agent. The distributions of the resulting oligomers (nx‐mers), which were quenched with methanol, were determined by a combination of gel permeation chromatography (GPC) and NMR. These distributions (presented by molar percentage) were conveniently calculated with the equation nx (mol %) = nx (% mol by GPC) × n0 (mol % by NMR)/n0 (% mol by GPC), where nx (% mol) = nx (wt % by GPC)/its molecular weight. The results showed the distributions of the preformed IPA/TPA‐BPA oligomers to be in fairly good accord with those obtained directly from GPC and to be supported by the NMR results. The calculation was applied to the co‐oligomers prepared up to a reaction of 0.7, at which there was an increase in the number of higher oligomers indivisible by GPC and the distributions could no longer be determined by molar percentage. The calculated distributions are discussed in relation to the results of copolycondensation. The sequence distributions in the resulting co‐oligomers, which were also examined by NMR, are compared with those in the copolymers. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 44–51, 2004 相似文献
25.
Zhaoqiang Lu Lin Cheng Jun Li Kai Zhang Song Yi Jingui Qin 《Journal of polymer science. Part A, Polymer chemistry》2004,42(4):925-932
The synthesis and structural characterization of a series of novel, fluorinated poly(phthalazinone ether)s containing perfluorophenylene moieties are described. The monomers, 4‐(4′‐hydroxyaryl)phthalazin‐1(2H)‐ones ( 2a – 2d ), were conveniently and efficiently synthesized from phenols and phthalic anhydride in two steps via 2‐(4′‐hydroxybenzoyl)benzoic acids, which were first obtained by the Friedel–Crafts reaction in good yields and with high stereoselectivity and were then converted into 2a – 2d by fusion with hydrazine. All the polymers were prepared by nucleophilic aromatic substitution (SNAr) polycondensation between the compounds perfluorobiphenyl and 4‐(4′‐hydroxyaryl)phthalazin‐1(2H)‐ones ( 2a ‐ 2d ). The resulting fluorinated polymers were readily soluble in common organic solvents (e.g., CHCl3, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, N‐methylpyrrolidone, etc.) at room temperature. Their weight‐average molecular weights and the polydispersities ranged from (7.96–18.25) × 103 to 1.31–2.71, respectively. Their glass‐transition temperatures varied from 213 to 263 °C. They were all stable up to 390 °C both in air and in argon. The 5% weight‐loss temperatures of these polymers in air and argon ranged from 393–487 to 437–509 °C, respectively. Wide‐angle X‐ray diffraction studies indicated they were all amorphous and could be attributed to the presence of kink nonplanar moiety, phenyl phthalazinone along the polymer backbone. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 925–932, 2004 相似文献
26.
27.
一类Narcissistic反应过渡态的优化 总被引:1,自引:0,他引:1
我们对一类narcissistic 反应XCH_2-CH_2Y→[过渡态TS]→YCH_2—CH_2X (1)进行了研究,结果表明其过渡态能在对称性限制下由能量极小化方法较容易地给出. 采用IMSPAK分子轨道从头算程序,在IBM VM/370计算机系统上用STO—3G极小基组以平衡几何构型的能量梯度优化方法,在对称性限制下对反应(1)的几种反应体系的过渡态构型进行了优化,其结果列于表1. 相似文献
28.
Bahattin Gümgüm Nermin Biricik Feyyaz Durap Ismail Özdemir Nevin Gürbüz Wee Han Ang Paul J. Dyson 《应用有机金属化学》2007,21(8):711-715
Palladium(II) complexes with N,N‐bis(diphenylphosphino)aniline ligands catalyse the Heck reaction between styrene and aryl bromides, affording stilbenes in good yield. The structures of two of the complexes used as pre‐catalysts have been determined by single‐crystal X‐ray diffraction. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
29.
《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(1):130-137
We have shown previously that iodosylbenzene–iron(III ) porphyrin intermediates ( 2 ) are generated in the reactions of oxoiron(IV ) porphyrin π‐cation radicals ( 1 ) and iodobenzene (PhI), that 1 and 2 are at equilibrium in the presence of PhI, and that the epoxidation of olefins by 2 affords high yields of epoxide products. In the present work, we report detailed mechanistic studies on the nature of the equilibrium between 1 and 2 in the presence of iodoarenes (ArI), the determination of reactive species responsible for olefin epoxidation when two intermediates (i.e., 1 and 2 ) are present in a reaction solution, and the fast oxygen exchange between 1 and H218O in the presence of ArI. In the first part, we have provided strong evidence that 1 and 2 are indeed at equilibrium and that the equilibrium is controlled by factors such as the electronic nature of iron porphyrins, the electron richness of ArI, and the concentration of ArI. Secondly, we have demonstrated that 1 is the sole active oxidant in olefin epoxidation when 1 and 2 are present concurrently in a reaction solution. Finally, we have shown that the presence of ArI in a reaction solution containing 1 and H218O facilitates the oxygen exchange between the oxo group of 1 and H218O and that the oxygen exchange is markedly influenced by factors such as ArI incubation time, the amounts of ArI and H218O used, and the electronic nature of ArI. The latter results are rationalized by the formation of an undetectable amount of 2 from the reaction of 1 and ArI through equilibrium that leads to a fast oxygen exchange between 2 and H218O. 相似文献
30.
The N-carboethoxy precursor to (±)-tecomanine has been prepared in 11 steps from 2-methyl-1-buten-3-yne. The key step, Pauson-Khand cyclization of a methylated 5-aza-6-nonen-1-yne succeeds, but only in low yield, a consequence of the dialkyl substitution about the azaenyne framework. Nevertheless, the overall sequence to that point is one of the more efficient to be described. 相似文献