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21.
A rhodium-catalyzed 1,4-addition of sodium tetraarylborates to β,β-disubstituted α,β-unsaturated esters has been developed. Highly efficient asymmetric catalysis has also been described to create quaternary carbon stereocenters at the β-position of esters by tuning the ester group of substrates and employing a readily available chiral diene ligand. 相似文献
22.
Shitomi Katayama Hideichi Horikawa Noboru Masuda 《Journal of polymer science. Part A, Polymer chemistry》1971,9(5):1173-1188
Anionic copolymerizations of acrylonitrile (monomer 1) with β-propiolactone (monomer 2) and the structures of the resulting copolymers were studied. The copolymerization with sodium cyanide in N,N-dimethylformamide gave copolymers of the structure I containing acid anhydride linkage in the molecular chains, with the monomer reactivity ratios, r1 = 1.20, r2 = 0.00. The copolymerization with potassium hydroxide gave either copolymers of the structure II (r1 = 0.00, r2 = 3.64 at 30°C; r1 = 0.00, r2 = 5.00 at 40°C) in N,N-dimethylformamide or only β-propiolactone homopolymer in toluene. 相似文献
23.
Murai K Morishita M Nakatani R Kubo O Fujioka H Kita Y 《The Journal of organic chemistry》2007,72(23):8947-8949
The first asymmetric total synthesis of spongotine A is described. The oxidative synthesis of the imidazoline/ketone unit from keto aldehyde and diamine is a key step in this synthesis. The absolute stereochemistry of the asymmetric center of natural spongotine A is revealed as the (S)-configuration. 相似文献
24.
We report calculations of the ground state energy and binding curve of the chromium dimer using the variational and diffusion quantum Monte Carlo (VMC and DMC) methods. We examined various single‐determinant and multideterminant wavefunctions multiplied by a Jastrow factor as a trial/guiding wavefunction for VMC/DMC. The molecular orbitals in the single determinants were calculated using restricted or unrestricted Hartree–Fock or density functional theory (DFT) calculations where five commonly used local (SVWN5), semilocal (PW91 and BLYP), and hybrid (B1LYP and B3LYP) functionals were examined. The multideterminant expansions were obtained from the generalized valence bond and (truncated) unrestricted configuration interaction with single and double excitations (UCISD) methods. We also examined a UCISD wavefunction in which UCISD expansions were added to the UB3LYP single‐determinant reference, and their coefficients were optimized at the VMC level. In addition to the wavefunction dependence, the effects of pseudopotentials and backflow transformation were also investigated. The UB3LYP single‐determinant and multideterminant wavefunctions were found to give the variationally best DMC energies within the framework of single‐determinant and multideterminants, respectively, though both the DMC energies were higher than twice the DMC atomic energy. Some of the VMC binding curves show a flat or quite shallow well bottom, which gets recovered deeper by DMC. All the DMC binding curves have a minimum indicating a bound state, but the unrestricted ones overestimate the equilibrium bond length. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2012 相似文献
25.
Arata Yajima Yuuma Kagohara Keisuke Shikai Ryo Katsuta Tomoo Nukada 《Tetrahedron》2012,68(6):1729-1735
The synthesis of two potent osteoclast-forming suppressing agents isolated from the Chinese mushroom Agrocybe chaxingu, demethylincisterol A3 and chaxine A, was accomplished using ergocalciferol as the starting material. Our methodology for the synthesis of demethylincisterol A3 and chaxine A featured the construction of a butenolide moiety by the intramolecular Horner–Wadsworth–Emmons reaction under Masamune–Roush conditions. This is the first reported synthesis of chaxine A. 相似文献
26.
Yoshida R Sakai T Ito S Yamaguchi T 《Journal of the American Chemical Society》2002,124(27):8095-8098
Self-oscillation of polymer chains in an aqueous solution has been achieved. The ruthenium catalyst for the Belousov-Zhabotinsky reaction was polymerized by using N-isopropylacrylamide and dissolved into the solution containing the BZ substrates. Periodical soluble-insoluble changes of the polymer chain were spontaneously induced by the BZ reaction. The conformational oscillations of the polymer were measured as the optical transmittance changes of the solution. This is the first report that rhythmical and reversible soluble-insoluble changes of polymer chains are realized under constant and homogeneous conditions. The transducing system from chemical energy of the BZ reaction to optical information has been constructed. 相似文献
27.
We report the results of in situ AFM measurements examining the phase transition of bilayers formed from the zwitterionic phospholipid, DMPC, 1,2-dimyristoyl-sn-glycero-3-phosphocholine, supported on mica. The images show that the fluid to gel phase transition process features substantial tearing of the bilayer due to the density change between the two phases. The gel to fluid transition is strongly affected by the resultant stress introduced into the gel phase, which changes the degree of cooperativity, the shape of developing fluid phase regions, and the course of the transition. 相似文献
28.
Dutz H Helbing K Krimmer J Speckner T Zeitler G Ahrens J Altieri S Annand JR Anton G Arends HJ Beck R Bock A Bradtke C Braghieri A v Drachenfels W Frommberger F Godo M Goertz S Grabmayr P Hasegawa S Hansen K Harmsen J Heid E Hillert W Holvoet H Horikawa N Iwata T Van Hoorebeke L d'Hose N Jennewein P Kiel B Klein F Kondratiev R Lang M Lannoy B Leukel R Lisin V Menze D Meyer W Michel T Naumann J Panzeri A Pedroni P Pinelli T Preobrajenski I Radtke E Reicherz G Rohlof C Rostomyan T Sauer M 《Physical review letters》2003,91(19):192001
To verify the fundamental Gerasimov-Drell-Hearn (GDH) sum rule for the first time experimentally, we measured the helicity dependent total photoabsorption cross section with circularly polarized real photons and longitudinally polarized nucleons in the photon energy range 0.68-1.82 GeV with the tagged photon facility at ELSA. The experiment was carried out with a 4pi detection system, a circularly polarized tagged photon beam, and a frozen spin polarized proton target. The contribution to the GDH sum rule in this photon energy range is [49.9+/-2.4(stat)+/-2.2(syst)] microb. 相似文献
29.
Kuzuya A Mizoguchi R Morisawa F Komiyama M 《Chemical communications (Cambridge, England)》2003,(6):770-771
Short RNA fragments containing single nucleotide polymorphism (SNP) sites have been selectively clipped out of substrate RNA by using complementary DNA having two acridine residues and Lu(III), and the genotype of the substrate is accurately and easily determined by mass analysis of these fragments. 相似文献
30.
Within the standard SIR model with spatial structure, we propose two models for the superspreader. In one model, superspreaders have intrinsically strong infectiousness. In other model, they have many social connections. By Monte Carlo simulation, we obtain the percolation probability, the propagation speed, the epidemic curve, the distribution of secondary infected and the propagation path as functions of population and the density of superspreaders. By comparing the results with the data of SARS in Singapore 2003, we conclude that the latter model can explain the observation. 相似文献