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991.
In this report, a phosphine-catalyzed [4 + 1] annulation between α,β-unsaturated imines and allylic carbonates is described. This reaction represents the first realization of catalytic [4 + 1] cyclization of 1,3-azadienes with in situ formed phosphorus ylides, which provides highly efficient and diastereoselective synthesis of 2-pyrrolines. 相似文献
992.
David E. Bergbreiter Haw-Lih Su Hisao Koizumi Jianhua Tian 《Journal of organometallic chemistry》2011,696(6):1272-6917
This paper describes how the nonpolar polymer polyisobutylene (PIB) can be used as a handle to prepare PIB-bound NHC ligands that are soluble in monophasic mixtures of mixed solvents but phase separable when such solvent systems are perturbed to be biphasic. The results here show that such PIB-bound NHC ligands can be used to synthesize useful palladium catalysts. In this paper, both PIB-bound analogs of an N,N′-bis(2,6-diisopropylphenyl) heterocyclic carbene and simpler N,N′-dialkyl heterocyclic carbene ligand were prepared and were successfully used to form palladium cross-coupling catalysts. The reactivity, recycling and reusability of these catalysts has been examined. 相似文献
993.
Yuan S Si H Fu A Chu T Tian F Duan YB Wang J 《The journal of physical chemistry. A》2011,115(5):940-947
Titanium silicalite-1 (TS-1) is an important catalyst for selective oxidation reactions. However, the nature and structure of the active sites and the mechanistic details of the catalytic reactions over TS-1 have not been well-understood, leaving a continuous debate on the genesis of active sites on the TS-1 surface in the literature. In this work, the location of Si vacancies and [Ti(OSi)(4)] and [Ti(OSi)(3)OH] sites in the MFI (Framework Type Code of ZSM-5 (Zeolite Socony Mobile-Five)) framework has been studied using a full ab initio method with 40T clusters with a Si:Ti molar ratio of 39:1. It was shown that the former four energetically favorable sites for Si vacancies are T6, T12, T4, and T8 and for Ti centers of [Ti(OSi)(4)] are T10, T4, T8 and T11, being partially the same sites. Whether by replacing Si vacancies or substituting the fully coordinated Si sites, the most preferential site for Ti is T10, which indicates that the insertion mechanism does not affect the favorable sites of Ti in the MFI lattice. For the defective [Ti(OSi)(3)OH] sites, it was found that the Si vacancy at T6 with a Ti at its neighboring T9 site (T6-def-T9-Ti pair) is the most energetically favorable one, followed by a T6-def-T5-Ti pair with a small energy gap. These findings are significant to elucidate the nature of the active sites and the mechanism of reactions catalyzed by TS-1 and to design the TS-1 catalyst. 相似文献
994.
We have studied C(2)H(4) and O(2) molecules separately or simultaneously for adsorption on V(n) (n = 2-8) clusters, and V(n) clusters catalyzed ethylene oxidation to acetaldehyde using spin-polarized density functional theory calculations. Molecular adsorption and clear size-dependent adsorption energy are predicted for C(2)H(4). O(2) is dissociately adsorbed with nearly constant adsorption energy. In the case of coadsorption, O(2) and C(2)H(4) adsorb on the V(n) surface simultaneously. Each keeps the same adsorption form, molecular or dissociative, as in separate adsorption. The noted cooperative effect is noted in C(2)H(4) and O(2) coadsorption, which activates the C-C double bond of C(2)H(4) and favors its oxidization. Furthermore, both the separate and coadsorptions result in magnetic enhancement or reduction of V(n), which is found to be dependent on the cluster size and the adsorbates. In addition, we reveal the reaction mechanism of V(2) (V(6))-catalyzed ethylene oxidation to acetaldehyde and find the overall reaction is exothermic and barrierless. 相似文献
995.
Tian J Ma S Thallapally PK Fowler D McGrail BP Atwood JL 《Chemical communications (Cambridge, England)》2011,47(27):7626-7628
Cucurbit[7]uril (CB[7]), in its amorphous solid state, shows one of the highest CO(2) sorption capacities among known organic porous materials at 298 K and 0.1 and 1 bar. In addition to the highest CO(2) capacity, CB[7] also shows remarkable selectivity of CO(2) over N(2) and CH(4). These properties, along with the existence of readily available precursors, indicate amorphous CB[7] might find applications in recycling CO(2) particularly considering the easy synthesis and potentially low manufacturing costs. 相似文献
996.
(S(p))-(+)-Spiniferin-1 and (R(p))-(-)-spiniferin-1, a pair of unusual marine natural products with planar chirality, were firstly synthesized via a polyfluoroalkanosulfonyl fluoride induced homoallylic carbocation rearrangement reaction. The chiral resolution and palladium-catalyzed β-H elimination of allylic alcohol derivatives were considered as the key steps of these divergent syntheses. 相似文献
997.
One pot production of 5-hydroxymethylfurfural with high yield from cellulose by a Brønsted-Lewis-surfactant-combined heteropolyacid catalyst 总被引:1,自引:0,他引:1
Zhao S Cheng M Li J Tian J Wang X 《Chemical communications (Cambridge, England)》2011,47(7):2176-2178
A Br?nsted-Lewis-surfactant-combined heteropolyacid (HPA) Cr[(DS)H(2)PW(12)O(40)](3) has been synthesized, and is used as a heterogeneous catalyst for the conversion of cellulose to 5-hydroxymethylfurfural in one pot within 2 h at 150 °C with 77.1% conversion and 52.7% yield. This micellar HPA catalyst shows stability and can be recycled by simple separation process. 相似文献
998.
Tian J Thallapally P Liu J Exarhos GJ Atwood JL 《Chemical communications (Cambridge, England)》2011,47(2):701-703
A well-known organic host, tris-o-phenylenedioxycyclotriphosphazene, exists in two polymorphic guest-free forms: the thermodynamic nonporous high-density phase and the kinetic nanoporous low-density phase. Simple pressurization of the high density phase with CO(2) brings a solid-state transformation to the low density phase, resulting in significant expansion of the crystal volume by 23%. 相似文献
999.
Ding T Tian Y Liang K Clays K Song K Yang G Tung CH 《Chemical communications (Cambridge, England)》2011,47(8):2429-2431
Oxygen plasma etching of electrospun polymer fibers containing spherical colloids is presented as a new approach towards anisotropic colloidal nanoparticles. The detailed morphology of the resulting nanoparticles can be precisely controlled in a continuous way. The same approach is also amenable to prepare inorganic nanoparticles with double-sided patches. 相似文献
1000.
Wang X Qi Z Wang S Liu G Gao H Tian Y 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2011,79(5):1660-1662
In order to investigate gastric cancer at cellular and sub-cellular level, a single human gastric adenocarcinoma BGC823 cell was studied by an infrared microscope equipped with a focal plane array (FPA) detector. The spectra showed difference between the nucleus and the endoplasmic reticulum (ER) of the BGC823 cell. The peak of vasPO2- was shifted to a higher wavenumber at the nucleus compared with that at the ER. The height ratios of 2954 cm(-1)/2922 cm(-1) (CH3/CH2) and 1088 cm(-1)/1539 cm(-1) (DNA/amide II) of the nucleus were significantly higher than those of the ER. Furthermore, chemical images reveal the intensity distributions of lipids, proteins and DNA of the single BGC823 cell, and the intense absorptions of proteins and DNA were observed in the nuclear region of the cell while the intense absorption of lipids was found in the ER region of the cell. The Fourier transform infrared (FTIR) microspectroscopic imaging result indicates the study of the single gastric cancer cell at sub-cellular level can be beneficial for knowing gastric cancer more which will be of great importance for the study and diagnosis of gastric cancer. The result also suggests that FPA is a useful tool in the study of a single cell and may be a powerful tool for study and diagnosis of gastric cancer. 相似文献