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1.
Several Diels-Alder adducts between benzoquinones and cyclopentadiene were reduced to the corresponding diols 7a-c and 11. Treatment of these diols with strong acid triggered a skeletal rearrangement reaction resulting in compounds 8a-c and 12 that contain a 4,8-methanoazulene substructure. In addition, a dyotropic-like rearrangement of the tetracyclic lactone 13 to the spiro-lactone 18 was observed. Five of the structures were supported by X-ray analysis. 相似文献
2.
Through the use of cyclic beta-diketones as supporting ligands, the copper-catalyzed coupling of aryl iodides with aliphatic amines occurs at room temperature in as little as 1 h. These high reaction rates allow for the coupling of a wide range of aryl and heteroaryl iodides at room temperature. This method is highly tolerant of a number of reactive functional groups, including -Br and aromatic -NH2 as well as phenolic and aliphatic -OH. The high selectivity of the CuI-beta-diketone catalyst for aliphatic amines represents a useful complement to the palladium-based methods. 相似文献
3.
《Current Opinion in Colloid & Interface Science》2007,12(3):129-137
Amphiphilic association in room-temperature ionic liquids (RT-ILs) — a “green” solvent shows analogies as well as clear differences from self-assembly in water. In this review, we summarize the known features of amphiphilic association structures in the form of micelles, microemulsions, vesicles and lyotropic liquid-crystalline phases in ionic liquids. Most of the methods making use of association to control reactivity could be developed also in RT-ILs and we give a few recently published examples of this strategy. 相似文献
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[reaction: see text] The presence of a suitable amount of bromide or chloride ions was found to be critical in forming the alkylzinc reagents from alkyl iodides and zinc metal in the room-temperature ionic liquid, N-butylpyridinium tetrafluoroborate. Beta-hydride transfer in the reactions of butylzinc reagents with aldehydes can also be reduced by a bromide ion. 相似文献
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Xiang-Yuan Li Quan Zhu Lin-Lin Zhao Shun-Qing Xiao Feng Liu 《Theoretical chemistry accounts》2002,107(5):282-290
Based on the spherical cavity approximation and the Onsager model, a dipole–reaction field interaction model has been proposed
to elucidate the solvent reorganization energy of electron transfer (ET). This treatment only needs the cavity radius and
the solute dipole moment in the evaluation of the solvent reorganization energy, and fits spherelike systems well. As an application,
the ET reaction between p-benzoquinone and its anion radical has been investigated. The inner reorganization energy has been calculated at the level
of MP2/6–31+G, and the solvent reorganization energies of different conformations have been evaluated by using the self-consistent
reaction field approach at the HF/6–31+G level. Discussions have been made on the cavity radii and the values are found to
be reasonable when compared with the experimental ones of some analogous intramolecular ET reactions. The ET matrix element
has been determined on the basis of the two-state model. The fact that the value of the ET matrix element is about 10 times
larger than RT indicates that this ET reaction can be treated as an adiabatic one. By invoking the classical Marcus ET model, a value of
4.9 × 107M−1s−1 was obtained for the second-order rate constant, and it agrees quite well with the experimental one.
Received: 19 October 2001 / Accepted: 17 January 2002 / Published online: 3 May 2002 相似文献
8.
N-Phenylurea was found to constitute a highly efficient, yet low-priced, phosphine-free ligand for the Pd-catalyzed Heck and room-temperature Suzuki reactions of aryl bromides and iodides with very high turnover numbers (ca. 103-104). 相似文献
9.
《Tetrahedron letters》1986,27(9):1015-1018
A short, convergent synthesis of (±)11,14-dimethoxypodocarpa-8,11,13-triene, 11, is described based on successful high pressure and Lewis acid catalyzed Diels-Alder reactions for the construction of the 4,4,10-trimethyloctahydrophenanthrene ring system. 相似文献
10.
Maegawa T Kitamura Y Sako S Udzu T Sakurai A Tanaka A Kobayashi Y Endo K Bora U Kurita T Kozaki A Monguchi Y Sajiki H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(20):5937-5943
A mild and efficient ligand-free Suzuki-Miyaura coupling reaction catalyzed by heterogeneous Pd/C was developed. Aryl bromides and triflates undergo the cross-coupling with aryl boronic acids in excellent yields without the presence of any additives in aqueous media at room temperature. Aryl vinyl boronic acids are also applicable to this coupling reaction and provide the trans-stilbene derivatives in high yields. The application of wet-type Pd/C to the coupling reaction was achieved without any loss of activity under aerobic conditions, and the reuse of Pd/C is feasible for a fifth run without significant loss of activity. Inductively coupled plasma (ICP) mass-spectrometric analysis of the filtrate from the reaction mixture of 4-bromonitrobenzene with phenylboronic acid demonstrated that the palladium metal hardly leached into the solution within the limits of the detector (<1 ppm), thus suggesting that the present Suzuki-Miyaura reaction proceeded by heterogeneous catalysis. 相似文献
11.
The ligand-dependent selectivities in Ullmann-type reactions of amino alcohols with iodobenzene by β-diketone- and 1,10-phenanthroline-ligated Cu(I) complexes were recently explained by the single-electron transfer and iodine atom transfer mechanisms (Jones, G. O., Liu, P., Houk, K. N., and Buchwald, S. L. J. Am. Chem. Soc. 2010, 132, 6205.). The present study shows that an alternative, oxidative addition/reductive elimination mechanism may also explain the selectivities. Calculations indicate that a Cu(I) complex with a negatively charged β-diketone ligand is electronically neutral, so that oxidative addition of ArI to a β-diketone-ligated Cu(I) prefers to occur (and occur readily) in the absence of the amino alcohol. Thus, coordination of the amino alcohol in its neutral form can only occur at the Cu(III) stage where N-coordination is favored over O-coordination. The coordination step is the rate-limiting step and the outcome is that N-arylation is favored with the β-diketone ligand. On the other hand, a Cu(I) complex with a neutral 1,10-phenanthroline ligand is positively charged, so that oxidative addition of ArI to a 1,10-phenanthroline-ligated Cu(I) has to get assistance from a deprotonated amino alcohol substrate. This causes oxidative addition to become the rate-limiting step in the 1,10-phenanthroline-mediated reaction. The immediate product of the oxidative addition step is found to undergo facile reductive elimination to provide the arylation product. Because O-coordination of a deprotonated amino alcohol is favored over N-coordination in the oxidative addition transition state, O-arylation is favored with the 1,10-phenanthroline ligand. 相似文献
12.
Soloshonok VA Cai C Hruby VJ Van Meervelt L Yamazaki T 《The Journal of organic chemistry》2000,65(20):6688-6696
Via the rational design of a single-preferred transition state, stabilized by electron donor-acceptor-type attractive interactions, structural and geometric requirements for the corresponding starting compounds have been determined. The Ni(II) complex of the Schiff base of glycine with o-[N-alpha-picolylamino]acetophenone, as a nucleophilic glycine equivalent, and N-(trans-enoyl)oxazolidin-2-ones, as derivatives of an alpha,beta-unsaturated carboxylic acid, were found to be the substrates of choice featuring geometric/conformational homogeneity and high reactivity. The corresponding Michael addition reactions were found to proceed at room temperature in the presence of catalytic amounts of DBU to afford quantitatively the addition products with virtually complete diastereoselectivity. Acidic decomposition of the products followed by treatment of the reaction mixture with NH4OH gave rise to the diastereomerically pure 3-substituted pyroglutamic acids. 相似文献
13.
《化学研究》2015,(5)
采用微波辅助加热还原法合成了钯/石墨烯(Pd/G)、钯/活性炭(Pd/AC)、钯/石墨(Pd/Graphite)和钯/二氧化硅(Pd/SiO2),并使用透射电子显微镜观测了钯的形貌及在载体上的分散性.将负载型钯催化剂用于苯醌加氢反应,结果显示,Pd/G催化剂的活性最高,苯醌的转化率达到99%,氢醌的选择性为100%,并且循环7次后催化剂仍保持着较高的转化率和选择性。结构表征表明,石墨烯担载的钯纳米粒子的粒径约为5nm,无明显团聚.实验进一步考察了反应溶剂(甲醇、乙醇、丙酮、正丙醇、异丙醇、正丁醇)对Pd/G催化苯醌加氢反应的影响,结果表明该反应对溶剂较为敏感,其中甲醇和丙酮较适宜作为反应溶剂.当以甲醇作为溶剂时,苯醌的转化率为98%,氢醌选择性为99%;以丙酮为溶剂时,苯醌转化率为98%,氢醌选择性为90%.研究工作表明,作为载体,石墨烯对钯催化剂的催化效果起着稳定和增强作用. 相似文献
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Kinetics of the addition reaction of triphenylphosphine to para‐benzoquinone in 1,2‐dichloroethane as solvent was studied. Initial rate method was used to determine the order of the reaction with respect to the reactants. Pseudo‐first‐order method was also used to calculate the rate constant. This reaction was monitored by UV‐vis spectrophotometry at 520 nm by variable time method. On the basis of the obtained results, the Arrhenius equation of this reaction was obtained: The activation parameters, Ea, ΔH#, ΔG#, and ΔS# at 300 K were 5.701, 6.294, 19.958 kcal mol?1 and ?45.853 cal mol?1 K?1, respectively. This reaction is first and second order with respect to triphenylphosphine and para‐benzoquinone, respectively. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 36:472–479, 2004 相似文献
16.
The sample-drying procedure described improves the precision, decreases the time needed and reduces the expense of the solid-surface room-temperature phosphorescence technique. Samples are dried in a glovebg apparatus interfaced to the sample compartment of the spectrophotophosphorimeter. The samples are treated with sodium citrate to prevent moisture quenching the phosphorescence emission The relative standard deviations of measurements are reduced to less than 2% for large sets of samples. The total time required for 37 samples is only 5.5 h compared to 20 h by a conventional technique. 相似文献
17.
Triphenylphosphine as a ligand for room-temperature Ni(0)-catalyzed cross-coupling reactions of aryl chlorides with arylboronic acids 总被引:2,自引:0,他引:2
Room-temperature Ni(0)-catalyzed cross-coupling reactions of deactivated aryl chlorides with arylboronic acids with inexpensive triphenylphosphine (PPh3) as a supporting ligand have been accomplished in good to excellent yields. Air-stable Ni(PPh3)2Cl2 has also been established as catalyst precursor, and highly active nickel catalysts were obtained when the reduction of Ni(PPh3)2Cl2 with n-BuLi was carried out in the presence of an aryl chloride. 相似文献
18.
Guo X Bruins AP Covey TR Trötzmüller M Lankmayr E 《Journal of the American Society for Mass Spectrometry》2009,20(1):105-111
Reduction of ionic chemical background noise based on selective gas-phase reactions with chosen neutral reagents has been
proven to be a very promising approach in liquid chromatography—mass spectrometry (LC-MS). In this study further investigations
on alternative reagents including the disulfides (dimethyl disulfide, diethyl disulfide, methyl propyl disulfide), dimethyl
trisulfide, ethylene oxide, and butadiene monoxide, for example, have been carried out. Tandem mass spectrometric studies
of ion/molecule reactions indicate that—besides dimethyl disulfide—ethylene oxide and butadiene monoxide also exhibit very
efficient reactions with background ions. Furthermore, it is confirmed that the reactions are very selective according to
the test with some analyte ions. In contrast to its rapid reactions with background ions, ethylene oxide does not react, or
reacts much less, with these analytes. Therefore, it can be used as an alternative reagent for noise reduction. Although reactions
of the other tested neutral reagents with background ions are evaluated, they are generally not suitable as reagents for this
purpose because of lack of reactivity or dramatic ion losses during reactions. 相似文献
19.
采用浸渍法制备了负载型高分散纳米Ru催化剂,利用X射线衍射、X射线光电子能谱、透射电子显微镜、N2吸附-脱附实验对催化剂进行了表征,结果显示,Ru以高分散金属态存在,其平均粒径在5nm左右。考察了不同酸碱介质、催化剂与底物物质的量的比、反应温度、H2压力和反应时间对对苯二酚收率的影响。结果表明,以盐酸为反应介质,以5%Ru/AC为催化剂,nRu/AC∶n对苯醌=1∶100,反应温度30℃,H2压力3.0MPa,反应时间30min,对苯二酚的收率可达97.5%。 相似文献
20.
This study investigated the room-temperature compression molding/particle leaching approach to fabricate three-dimensional porous scaffolds for tissue engineering. Scaffolds with anatomical shapes (ear, joint, tube, cylinder) were made from biodegradable poly(D,L-lactide) and poly[(D,L-lactide)-co-glycolide]. The utility of this room-temperature compression approach comes from the effect of solvent assistance, but the tendency for post-molding scaffold shrinkage is a problem unique to this method and is thus examined with emphasis in this paper. Scaffold shrinkage was found to be tolerable under normal fabrication conditions with high salt contents, which is just what the preparation of highly porous scaffolds requires. Furthermore, the resultant porosities after salt leaching were measured as well as the initial scaffold shrinkages after solvent evaporation, and the relation between them was revealed by theoretical analysis and confirmed by comparison with experimental measurements. The pores were interconnected, and porosity can exceed 90%. The effects of porosity on the mechanical properties of porous scaffolds were also investigated. This convenient fabrication approach is a prospective method for the tailoring of porous scaffolds for a variety of possible applications in tissue engineering and tissue reconstruction. 相似文献