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51.
G. N. Merrill 《Journal of Physical Organic Chemistry》2007,20(1):19-29
Ab initio molecular orbital calculations were carried out on epibromohydrin (EBH) and epichlorohydrin (ECH) in an attempt to elucidate their reactivity with respect to a hard nucleophile, hydroxide. These systems were modeled in both the gas phase and a polar solvent under basic conditions. In the gas phase, it was determined that a direct displacement mechanism (nucleophilic attack at the C1 position) was operative for EBH, while an indirect pathway (nucleophilic attack at the C3 position and subsequent intramolecular displacement) was followed for ECH. In an acetone solution, only the indirect displacement mechanism was found to occur. An electrostatic argument is advanced to account for this behavior in polar solution. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
52.
Vicenç Branchadell Roser Pleixats Claude Commandeur Max Malacria 《Journal of organometallic chemistry》2003,687(2):337-345
Regioselectivity of the Tsuji-Trost reaction on allyl acetates and carbonates substituted with silyl groups at the olefinic moiety has been analyzed. Silicon atom in the central carbon atom increases the stability of the intermediate π-allylpalladium cation with respect to the isomeric π-allylpalladium cation featuring the silicon in a terminal carbon atom. 相似文献
53.
Arata Yajima Ayumi Yamaguchi Fumihiro Saitou Tomoo Nukada Goro Yabuta 《Tetrahedron》2007,63(5):1080-1084
A convergent synthetic strategy for abietane diterpenoids via B-alkyl Suzuki-Miyaura coupling and Lewis acid-mediated cyclization reactions is established. Asymmetric total synthesis of 12-deoxyroyleanone, an antileishmanial diterpene, is described. 相似文献
54.
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56.
潘继斌 《数学的实践与认识》2006,36(2):182-185
研究了基于支持向量机的后验概率的应用,提出了对样本集进行分解,以产生局部后验概率,根据模式的稳健性对局部后验概率进行凸组合融合的方法. 相似文献
57.
We analyze the statistical behavior of signals in nonlinear circuits with delayed feedback in the presence of external Markovian noise. For the special class of circuits with intense phase mixing we develop an approach for the computation of the probability distributions and multitime correlation functions based on the random phase approximation. Both Gaussian and Kubo-Andersen models of external noise statistics are analyzed and the existence of the stationary (asymptotic) random process in the long-time limit is shown. We demonstrate that a nonlinear system with chaotic behavior becomes a noise amplifier with specific statistical transformation properties. 相似文献
58.
Surajit Some 《Tetrahedron letters》2006,47(7):1221-1224
A convenient synthetic approach to substituted benzene derivatives by modified Ullmann cross-coupling of 2-bromobenzaldehyde and bromovinylaldehydes followed by intramolecular McMurry coupling has been developed. 相似文献
59.
Gianluigi Luppi Rodrigo J. Corrêa Angelo C. Pinto Quirinus B. Broxterman Claudia Tomasini 《Tetrahedron》2006,62(51):12017-12024
The first total synthesis of (R)-convolutamydine A has been achieved by the organocatalytic addition of acetone to 4,6-dibromoisatin. The absolute configuration was determined by single crystal X-ray diffraction. DFT studies were used to model the transition states for the aldol reaction and equilibrium geometries of the post-aldol reaction intermediates. The DFT study revealed that the aldol bond forming reaction was considerably endothermic. 相似文献
60.
Thomas Marlow 《International Journal of Theoretical Physics》2006,45(7):1247-1257
We attempt a justification of a generalisation of the consistent histories programme using a notion of probability that is valid for all complete sets of history propositions. This consists of introducing Cox's axioms of probability theory and showing that our candidate notion of probability obeys them. We also give a generalisation of Bayes' theorem and comment upon how Bayesianism should be useful for the quantum gravity/cosmology programmes.
PACS: 02.50.Cw;03.65.Ta;04.60.-m. 相似文献