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91.
Didier Bruyère 《Journal of organometallic chemistry》2003,687(2):466-472
The results of our preliminary investigations directed toward asymmetric catalysis of the cyclocarbopalladation of alkenes bearing a proximate nucleophile with organic halides (or triflates) are disclosed. A series of bidentate phosphine ligands were evaluated in intramolecular versions of this reaction using (E)-2-[7-(2-bromophenyl)-hept-4-enyl]-malonic acid dimethyl ester (1) and (Z)-2-[7-(2-trifluoromethanesulfonyloxy-phenyl)-hept-4-enyl]-malonic acid dimethyl ester (9) as model substrates. The highest enantioselective induction was obtained with aryl triflate 9 which produced the corresponding cyclopentylindane as a single diastereomer in 54% chemical yield and 43% ee by using PdCl2[S-(−)-TolBINAP] as chiral catalyst and K2CO3 as base. 相似文献
92.
研究了过渡金属催化的炔烃衍生物的异构化反应.从α,β-炔酮、2-炔酸酯和2-炔酸酰胺可以生成相应的(E,E)-共轭双烯酮、双烯酸酯和双烯酸酰胺.首次从2-炔醇异构化为相应的2-烯酮或2-烯醛.这一反应具有简单、高产率和立体选择性的优点.假设反应烯经过连二烯中间体,然后再异构化成产物,这一反应提供了方便而有潜在应用价值的方法以制备天然产物合成时的重要中间体. 相似文献
93.
[TPPFe(III)]~2O的合成及其对细胞色素P-450的模拟 总被引:3,自引:0,他引:3
TPPFe(III)Cl通过中性Al~2O~3色谱柱得到一个新化合物, 它在HPLC中的保留时间比TPPFe(III)Cl大得多, IR、UV-Vis和元素分析表明, 这个新化合物是[TPPFe(III)]~2O. 同TPPFe(III)Cl一样, 它具有在常温常压下催化碳氢化合物单充氧化的性质。[TPPFe(III)]~2O催化下PhIO氧化环己烷的反应, 在CH~2Cl~2和环己烷介质中, 氧化产率分别为14.97和62.6%, 高于TPPFe(III)Cl作催化剂时的产率。在环己烷溶剂中, 反应产率与反应时间呈线性关系, 且反应有大约3小时诱导期。但在CH~2Cl~2溶剂中不存在反应产物与时间的线性关系, 也不存在诱导期。与TPPFe(III)Cl比较,[TPPFe(III)]~2O对氧化剂更稳定。上述事实表明, [TPPFe(III)]~2O能够作为细胞色素P-450的模型化合物。 相似文献
94.
Pullin等人曾对全氟碘代烷与三级胺的相互作用进行了研究,发现R_(?)I与NR_3能形成电荷转移络合物,即:R_(?)…I…NR_3。但此后却未见到有关反应的报道。我们发现在钯催化剂存在下,全氟碘化物与三乙胺能发生反应,反应条件较为温和,产物为氟代烷基烯基二乙基胺1。反应可能是在三乙胺中先产生一个双键,然后β碳原子接上一个全氟烷基。1的IR和NMR与Blanc报道的一致。化合物1经水解可得胺基烯酮2。在酸溶液中水解时,速度明显加快,而在碱溶液中,不仅不能加快水解速度,而且还有副反应发生。我们对化合物2进 相似文献
95.
A new synthetic route for the preparation of the betain-like compound (CH3N)6P4F8 from (CH3NPF3)2,N-methyl-hexamethyldisilazane andN,N-dimethyl-urea has been found. The steps of this multi-stage reaction could be rationalized to a far extent.
10. Mitteilung:Kubjacek M., Utvary K., Mh. Chem.112, 305 (1981). 相似文献
96.
The stereochemistry of substituted cyclopent-2-en-1-ones was studied by NMR. The existence of non-planar rings is indicated and conformational analysis, based principally upon examination of the coupling constants enables the conformational population to be estimated; trans dihalogeno derivatives, for example, occur predominantly in the diaxial form. 相似文献
97.
Kihyun Cho Jangwon Oh Taewon Lee Dongwook Shin 《Journal of Analytical and Applied Pyrolysis》2007,80(2):502-506
Aerosol flame pyrolysis deposition method was applied to deposit the oxide glass electrolyte film and LiCoO2 cathode for thin film type Li-ion secondary battery. The thicknesses of as-deposited porous LiCoO2 and Li2O–B2O3–P2O5 electrolyte film were about 6 μm and 15 μm, respectively. The deposited LiCoO2 was sintered for 2 min at 700 °C to make partially densified cathode layer, and the deposited Li2O–P2O5–B2O3 glass film completely densified by the sintering at 700 °C for 1 h. After solid state sintering process the thicknesses were reduced to approximately 4 μm and 6 μm, respectively. The cathode and electrolyte layers were deposited by continuous deposition process and integrated into a layer by co-sintering. It was demonstrated that Aerosol flame deposition is one of the good candidates for the fabrication of thin film battery. 相似文献
98.
99.
Geometries and stabilization energies of various simple H-bonded complexes (water dimer, hydrogen fluoride dimer, formamide
dimer, formic acid dimer) have been determined by a gradient optimization that eliminates the basis set superposition error
(BSSE) by the counterpoise (CP) method in each gradient cycle as well as by the standard gradient optimization. Both optimization
methods lead to different potential energy surfaces (PES). The difference depends on the theoretical level used and is larger
if correlation energy is considered. Intermolecular distances from the CP-corrected PES are consistently longer, and this
difference might be significant (∼0.1 ?); also angular characteristics determined from both surfaces differ significantly.
Different geometries were obtained even when passing to larger basis sets (aug-cc-pVDZ). The standard optimization procedure
can result in a completely wrong structure. For example, the “quasi-linear” structure of the (HF)2 (global minimum) does not exist at the standard MP2/ 6-31G** PES (where only cyclic structure was detected) and is found
only at the CP-corrected PES. Stabilization energies obtained from the CP-corrected PES are always larger than these from
the standard PES where the BSSE is added only a posteriori for the final optimized structure; both energies converge only
when passing to a larger basis set (aug-cc-pVDZ).
Received: 11 March 1998 / Accepted: 19 June 1998 / Published online: 4 September 1998
RID="
ID=" <E6>Acknowledgements.</E6> The project was supported by the Grant Agency of the Czech Republic (Grant No. 203/98/1166).
RID="
ID=" <E5>Correspondence to</E5>: P. Hobza 相似文献
100.
Poverenov E Gandelman M Shimon LJ Rozenberg H Ben-David Y Milstein D 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(19):4673-4684
Novel anionic dialkyl, diaryl, and dihydride platinum(II) complexes based on the new "long-arm" hemilabile PCN-type ligand C6H4[CH2P(tBu)2](CH2)2N(CH3)2 with the general formula Li+[Pt(PCN)(R)2]- (R=Me (4), Ph (6) and H (9)) were prepared by reaction of [Pt(PCN)(R)] complexes (obtained from the corresponding chlorides) with an equivalent of RLi, as a result of the opening of the chelate ring. Alkylating agents based on other metals produce less stable products. These anionic d8 complexes are thermally stable although they bear no stabilizing pi acceptors. They were characterized by 1H, 31P[1H], 13C, and 7Li NMR spectroscopy; complex 9 was also characterized by single crystal X-ray crystallography, showing that the Li+ ion is coordinated to the nitrogen atom of the open amine arm and to the hydride ligand (trans to the P atom) of a neighboring molecule (H--Li=2.15 A), resulting in a dimeric structure. Complexes 4 and 9 exhibit high nucleophilic reactivity, upon which the pincer complex is regenerated. Reaction of 4 with water, methyl iodide, and iodobenzene resulted in the neutral complex [Pt(PCN)(CH3)] (3) and methane, ethane, or toluene, respectively. Labeling studies indicate that the reaction proceeds by direct electrophilic attack on the metal center, rather than attack on the alkyl ligand. The anionic dihydride complex 9 reacted with water and methyl iodide to yield [Pt(PCN)(H)] (8) and H2 or methane, respectively. 相似文献