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11.
Nakamura S Yonehara M Uchiyama M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(4):1068-1078
Silylmetalation of alkenes is challenging due to the low reactivity of the substrates. In contrast, carbometalation of alkenes has been realized through several innovative methods, including activation of the reagent and the substrate. A similar approach could be applicable to silylmetalation of alkenes, and we have recently developed a bimetal activation method using zincate complexes for this purpose. Here, we describe how the silylzincation of alkenes was achieved. First, the strategies for carbometalation of alkenes will be summarized. Secondly, the history and development of silylzincation chemistry are briefly described. Then the details of our findings related to two types of silylzincation of alkenes, as well as recent progress in mechanistic studies, are discussed. The key point in the silylzincation of alkenes proved to be the bimetal activation of the substrate. One metal (copper or titanium) strongly coordinates and activates the alkene moiety, and the other metal (zinc) acts as the electron acceptor from the silyl group by way of the alkene moiety. This dual activation concept is expected to be applicable to other combinations of metals, as well as to new types of reactions. 相似文献
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Micron-sized, monodispersed polystyrene (PS)/poly (n-butyl methacrylate) (PBMA) composite particles, in which the PS domain(s) were dispersed in a PBMA continuous phase, were
produced by seeded polymerization for dispersions of n-butyl methacrylate (BMA) swollen PS particles in a wide range of PS/BMA ratios in the presence of NaNO2 as a water-soluble inhibitor. Moreover, in order to change the diameter of the composite particles at same PS/BMA ratio,
PS/PBMA (1/150 w/w) composite particles were produced using five kinds of PS particles in a range of diameters from 0.64 to
3.27 μm as seeds. The percentages of the PS/PBMA composite particles having double and triple and over PS domains, which were
thermodynamically unstable morphologies, increased with the increase in the diameter of BMA swollen PS particles. There was
a clear influence of the size of the swollen particles on the morphology of the PS/PBMA composite particles produced.
Received: 30 September 1999/Accepted: 18 April 2000 相似文献
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A novel amphiphilic phosphinite-oxazoline chiral compound, 2-methyl-4,5-[4,6-O-benzylidene-3-O-bis[4-((diethylamino)methyl)phenyl]phosphino-1,2-dideoxy-alpha-D-glucopyranosyl]-[2,1-d]-2-oxazoline (1), has been prepared from natural D-glucosamine hydrochloride. The newly prepared complex, [Pd(2-methyl-4,5-[4,6-O-benzylidene-3-O-bis[(4-((diethylmethylammonium)methyl)phenyl)]phosphino-1,2-dideoxy-alpha-D-glucopyranosyl]-[2,1-d]-2-oxazoline)(eta3-C3H5)]3+ x 3BF4- (3), is soluble in water and an efficient catalyst for asymmetric allylic substitution reaction in water or an aqueous/organic biphasic medium (up to 85% ee). This catalytic system offers an easy separation of the aqueous catalyst phase from the product phase and allows recycling of the catalyst phase. In addition, compound 1 also works as an effective ligand for the palladium-catalyzed reaction under conventional homogeneous conditions in an organic medium, in which the catalyst (Pd-1 complex) can be recovered by simple acid/base extraction and reused in the second reaction. 相似文献
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Y. Arimoto N. Shimakura K. Yonehara T. Yamagata M. Tanaka 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2000,8(3):305-308
The spin-exchange cross-section, , was measured for a 6.33 keV/amu He ion incident on a polarized Rb atom. The result is cm2, which is unexpectedly an order of magnitude smaller than the theoretical value cm2 evaluated by the semiclassical impact parameter method assuming formation of a single molecular state.
Received 11 September 1999 and Received in final form 28 December 1999 相似文献
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The method involves the measurement of the extent of the induced reaction, which ceases a few seconds after initiation. Antimony(III) can be determined in the range 0.4–10 μg ml-1. The standard deviation is ±0.25 μg. The method is applied to marine sediments. 相似文献
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Yonehara F Kido Y Sugimoto H Morita S Yamaguchi M 《The Journal of organic chemistry》2003,68(17):6752-6759
GaCl(3) catalyzes the aromatic alkylation of naphthalene or phenanthrene using cycloalkanes. The C[bond]C formation predominantly takes place at the least hindered positions of the substrates, and equatorial isomers regarding the cycloalkane moiety are generally obtained. The reaction of bicyclo[4.4.0]decane and naphthalene occurs at the 2-position of naphthalene and at the 2- or 3-carbons of the cycloalkane, and the products possess a trans configuration at the junctures and an equatorial configuration at the naphthyl groups. Notably, cis-bicyclo[4.4.0]decane turns out to be much more reactive than the trans isomer, and a turnover number "TON" up to 20 based on GaCl(3) is attained. 1,2-Dimethylcyclohexane reacts similarly, and the cis isomer is more reactive than the trans isomer. Monoalkylcycloalkanes react at the secondary carbons provided that the alkyl group is smaller than tert-butyl. Adamantanes react at the tertiary 1-position. The alkylation reaction is considered to involve the C[bond]H activation of cycloalkanes with GaCl(3) at the tertiary center followed by the migration of carbocations and electrophilic aromatic substitution yielding thermodynamically stable products. The stereochemistry of the reaction reveals that GaCl(3) activates the equatorial tertiary C[bond]H rather than the axial tertiary C[bond]H. 相似文献
17.
Morozov VS Etienne ZB Kandes MC Krisch AD Leonova MA Sivers DW Wong VK Yonehara K Anferov VA Meyer HO Schwandt P Stephenson EJ von Przewoski B 《Physical review letters》2003,91(21):214801
We recently studied spin flipping of a 270 MeV vertically polarized deuteron beam stored in the Indiana University Cyclotron Facility Cooler Ring. We adiabatically swept an rf solenoid's frequency through an rf-induced spin resonance and observed its effect on the deuterons' vector and tensor polarizations. After optimizing the resonance crossing rate and maximizing the solenoid's voltage, we measured a vector spin-flip efficiency of 94.2%+/-0.3%. We also found striking behavior of the spin-1 tensor polarization. 相似文献
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