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1.
α-Vinylfurans were obtained by phosphine-initiated cyclization of various enynes bearing a carbonyl group at the ene end in the presence of various aldehydes, in moderate to high yields. The reaction may consist of 1,6-addition of phosphine to the enynes, ring closure, and Wittig reaction between the ylid resulting from cyclization and an aldehyde. Thus, various aldehydes were able to be used in the reaction. The reaction was influenced greatly by the substituents at the acetylene position (R1) and the α-position of the carbonyl group (R3).  相似文献   
2.
LetM be a complete smooth surface of constant mean curvature in the Euclidean 3-space. If there exists two helical geodesics onM through each point ofM, thenM is either a plane, a sphere, or a circular cylinder.  相似文献   
3.
Kushida and Kushida found that FM radio waves from stations at distances over-the-horizon are received before earthquakes. Based on this finding, since the mid-1990’s, the Kushidas have been practicing “Earthquake Precursor Detection Experiment”. The performance of the Kushida method during 2000–2003 has been evaluated by checking their predictions against the actual seismicity. During the period, there were 92 Kushida predictions mentioning the possibility of M ≥ 5.5 event, whereas there were 49 M ≥ 5.5 earthquakes in the Japanese region. If the criteria for successful prediction are set as: the errors in date is less than one day, epicentral position is roughly within specified area, and error in M is less than 0.5, the success rate was 20% and the alarm rate was 12%. If we relax the criteria to: the errors in dates within 10 days, epicenter within additional 100 km of specified area and the magnitude error less than 1.0, the success rate was 40% and the alarm rate was 27%. These rates may look insufficient for a practical prediction method. Considering, however, the fact that no other short-term prediction has ever been made in Japan so far it is a significant achievement. Moreover, it was found that in almost all failed predictions, meaningful signals were detected although the interpretations were incorrect. This indicates that the method is promising provided further investigation is carried out. The same evaluation at the M ≥ 6.0 level showed that the general performance was similar to the M ≥ 5.5 level, except that both success rate and alarm rate were lower at the M ≥ 6.0 level. If this unexpected finding is real, it might be inherent to the methodology using scattering of short-wave length radio waves as suggested by M. Hayakawa and may contain important information in understanding the earthquake physics and LAI-coupling. The results of the present study indicate strongly that the earthquake prediction research using anomalous transmission of VHF FM radio waves should be enhanced in parallel with complementary research in other frequency ranges.  相似文献   
4.
Reversible formation of F+-centers was observed over platinum promoted sulfated zirconia in the presence and absence of hydrogen. The intensity of ESR signal of F+-centers was increased by treatment in He stream and it was decreased rapidly by supply of hydrogen in gas phase. This behavior seems to be related to proton spillover.  相似文献   
5.
Chiral 1-substituted isoquinoline derivatives, which were obtained by the reaction using alanine derivatives as chiral auxiliaries, were transformed to (S)-2,3,9,10,11-pentamethoxyhomoprotoberberine (7) and a synthetic intermediate for O-methylkreysigine (9) in good yields and high stereoselectivity. The corresponding chiral allyl derivative of isoquinoline was transformed to a pyrrolidinoisoquinoline (16) in a highly enantioselective manner.  相似文献   
6.
Metalated O-silyl cyanohydrins of beta-silyl-alpha,beta-epoxyaldehyde have been found to serve as functionalized homoenolate equivalents by a tandem sequence involving base-promoted ring opening of the epoxide, Brook rearrangement, and alkylation of the resulting allylic anion. On the basis of mechanistic studies involving competitive experiments using the diastereomeric cyanohydrins, we propose a reaction pathway involving a silicate intermediate 36 formed by a concerted process via an anti-opening of the epoxide followed by the formation of an O-Si bond.  相似文献   
7.
An ab initio electronic wave-packet dynamics coupled with the simultaneous classical dynamics of nuclear motions in a molecule is studied. We first survey the dynamical equations of motion for the individual components. Reflecting the nonadiabatic dynamics that electrons can respond to nuclear motions only with a finite speed, the equations of motion for nuclei include a force arising from the kinematic (nuclear momentum) coupling from electron cloud. To materialize these quantum effects in the actual ab initio calculations, we study practical implementation of relevant electronic matrix elements that are related to the derivatives with respect to the nuclear coordinates. Applications of the present scheme are performed in terms of the configuration state functions (CSF) using the canonical molecular orbitals as basis functions without transformation to particular diabatic basis. In the CSF representation, the nonadiabatic interaction due to the kinematic coupling is anticipated to be rather small, and instead it should be well taken into account through the off-diagonal elements of the electronic Hamiltonian matrix. Therefore it is expected that the nonadiabatic dynamics based on this CSF basis neglecting the kinematic coupling may work. To verify this anticipation and to quantify the actual effects of the kinematic coupling, we compare the dynamics with and without the kinematic-coupling terms using the same CSF set. Applications up to the fifth electronically excited states in a nonadiabatic collision between H(2) and B(+) shows that the overall behaviors of these two calculations are surprisingly similar to each other in an average sense except for a fast fluctuation reflecting the electronic time scale. However, at the same time, qualitative differences in the collision events are sometimes observed. Therefore it turns out after all that the kinematic-coupling terms cannot be neglected in the CSF-basis representation. The present applications also demonstrate that the nonadiabatic electronic wave-packet dynamics within ab initio quantum chemical calculation is feasible.  相似文献   
8.
Michael addition reactions of acetoacetates and malonates with acrylates in a 5 M KOH aqueous solution without using any other catalysts are described. When they are either tert-butyl or benzyl esters, the reaction proceeded very rapidly to afford moderate to high yields of the corresponding bis-Michael adducts that are unexpectedly stable under these conditions.  相似文献   
9.
10.
Sasaki M  Takeda K 《Organic letters》2004,6(26):4849-4851
[reaction: see text] Reaction of gamma-p-toluenesulfonyl-alpha,beta-epoxysilane with alkyl halides and aldehydes followed by treatment with n-Bu4NF affords alpha,beta-unsaturated aldehydes via a Brook rearrangement-mediated tandem process under extremely mild conditions.  相似文献   
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