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571.
Takanori Shibata Mayu Miyoshi Toshifumi Uchiyama Kohei Endo Nobuaki Miura Kenji Monde 《Tetrahedron》2012,68(12):2679-2686
An enantioselective intramolecular [2+2+2] cycloaddition of 2-aminophenol-tethered triynes and diyne-nitriles proceeded using the chiral Rh catalysts, and tripodal cyclophanes and pyridinophanes with a long ansa chain (up to [16]pyridinophane) were obtained in acceptable yield with high to almost perfect ee. In the reaction of triynes, we elucidated that the oxygen atom at the alkyne terminus is essential for the excellent enantioselectivity. For the construction of cage-type molecule, the choice of rigid tether, which connects 1,6-diyne moiety with a side carbon chain having alkyne or cyano group on its terminus, was important, and 8-amino-2-naphthol moiety was also a preferable tether. 相似文献
572.
In this study, we achieved the first total synthesis of (+)-heteroplexisolide E. The synthetic highlights of our approach include a one-pot regioselective methylation method and the transformation of a β-methallyl alcohol moiety to a prenyl group using palladium-catalyzed hydrogenolysis. 相似文献
573.
Yuko Otani Tatsuto Kiwada Atsuya Muranaka Masanobu Uchiyama Tomohiko Ohwada 《Tetrahedron》2006,62(50):11635-11644
In this report, we explore the feasibility of using bicyclic chiral β-amino acids, (1R,2R,4S)- and (1S,2S,4R)-7-azabicyclo[2.2.1]heptane-2-carboxylic acid (R-Ah2c and S-Ah2c, respectively), to prepare novel peptides with unique properties. Facile cis-trans isomerization of the non-planar amide bonds of these β-amino acids should result in great flexibility of the backbone structure of β-peptides containing them. Indeed, oligomers of these amino acids showed thermostability and characteristic CD absorptions, which were not concentration-dependent, suggesting that the oligomers remained monomeric. The results indicated the formation of self-organized monomeric structures with chain-length-dependent stabilization. Energy calculations suggested that the peptides can take helical structures in which the energy barriers to cis-trans isomerization are greater for the central amide bonds than for the terminal amides. 相似文献
574.
Kato T Okamoto I Tanatani A Hatano T Uchiyama M Kagechika H Masu H Katagiri K Tominaga M Yamaguchi K Azumaya I 《Organic letters》2006,8(22):5017-5020
An effective screening method combining parallel synthesis and solid-state CD measurements was established to identify achiral aromatic sulfonamides that show spontaneous resolution with rapidity. We found that 4 of the 12 achiral sulfonamides crystallized as chiral crystals through this method. The chirality of each sulfonamide was discriminated by solid-state CD spectra and Flack parameter in an X-ray analysis. Correspondence between the observed Cotton effect and the absolute configuration could be confirmed by time-dependent DFT calculations. [structure: see text] 相似文献
575.
The unusual fluorescence properties of 8-methoxy-4-methyl-2H-benzo[g]chromen-2-one (1) are described. The fluorophore 1 is almost nonfluorescent in aprotic solvent (e.g., fluorescence quantum yield Phi(f) < 0.0003 in n-hexane), whereas it strongly fluoresces at long wavelengths (>450 nm) in protic solvent (e.g., Phi(f) = 0.21 in methanol). The fluorophore 1 also shows good applicability in developing a new fluorogenic (fluorescent "off-on") sensor. [structure: see text] 相似文献
576.
On the Isolated Points of the Spectrum of Paranormal Operators 总被引:1,自引:0,他引:1
Atsushi Uchiyama 《Integral Equations and Operator Theory》2006,55(1):145-151
For paranormal operator T on a separable complex Hilbert space
we show that (1) Weyl’s theorem holds for T, i.e., σ(T) \ w(T) = π00(T) and (2) every Riesz idempotent E with respect to a non-zero isolated point λ of σ(T) is self-adjoint (i.e., it is an orthogonal projection) and satisfies that ranE = ker(T − λ) = ker(T − λ)*. 相似文献
577.
Takayuki Tanimoto Assoc. Prof. Mineto Uchiyama Prof. Masami Kamigaito 《Angewandte Chemie (International ed. in English)》2023,62(43):e202307791
A series of exo-olefin compounds ((CH3)2C(PhY)−CH2C(=CH2)PhY) were prepared by selective cationic dimerization of α-methylstyrene (αMS) derivatives (CH2=C(CH3)PhY) with p-toluenesulfonic acid (TsOH) via β-C−H scission. They were subsequently used as reversible chain transfer agents for sulfur-free cationic RAFT polymerization of αMS via β-C−C scission in the presence of Lewis acid catalysts such as SnCl4. In particular, exo-olefin compounds with electron-donating substituents, such as a 4-MeO group (Y) on the aromatic ring, worked as efficient cationic RAFT agents for αMS to produce poly(αMS) with controlled molecular weights and exo-olefin terminals. Other exo-olefin compounds (R−CH2C(=CH2)(4-MeOPh)) with various R groups were prepared by different methods to examine the effects of R groups on the cationic RAFT polymerization. A sulfur-free cationic RAFT polymerization also proceeded for isobutylene (IB) with the exo-olefin αMS dimer ((CH3)2C(Ph)−CH2C(=CH2)Ph). Furthermore, telechelic poly(IB) with exo-olefins at both terminals was obtained with a bifunctional RAFT agent containing two exo-olefins. Finally, block copolymers of αMS and methyl methacrylate (MMA) were prepared via mechanistic transformation from cationic to radical RAFT polymerization using exo-olefin terminals containing 4-MeOPh groups as common sulfur-free RAFT groups for both cationic and radical polymerizations. 相似文献