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31.
Naoyuki Shimada 《Tetrahedron letters》2010,51(50):6572-6575
A catalytic asymmetric synthesis of descurainin has been achieved by incorporating an enantioselective 1,3-dipolar cycloaddition, a stereoselective alkene hydrogenation, an oxidation with Fremy’s salt and a regioselective demethylation with NbCl5 as the key step. The 1,3-dipolar cycloaddition of a carbonyl ylide derived from tert-butyl 2-diazo-5-formyl-3-oxopetanoate with 4-hydroxy-3-methoxyphenylacetylene in the presence of dirhodium(II) tetrakis[N-tetrachlorophthaloyl-(R)-tert-leucinate], Rh2(R-TCPTTL)4, provided an 8-oxabicyclo[3.2.1]octane skeleton in 95% ee. 相似文献
32.
Mitsushiro Nomura Shigemi Kondo Eriko Suzuki Glenn V. Alea Chikako Fujita-Takayama Masatsugu Kajitani 《Journal of organometallic chemistry》2010,695(21):2366-2895
Eight new sulfur-rich [CpCo(dithiolene)] complexes were synthesized from [Zn(dmit)2]2− as a starting material. The structures, electrochemical behavior and electronic absorption spectra of the sulfur-rich [CpCo(S2C2S2Y)] complexes could be compared with the early data of analogous Ni complexes. [CpCo(pddt)] (Y = -(CH2)3-), [CpCo(dpdt)] (Y = -CH2C(CH2)CH2-), [CpCo(bddt)] (Y = -(CH2)4-), [CpCo(dtdt)] (Y = -CH2SCH2-) and [CpCo(poddt)] (Y = -CH2C(O)CH2-) crystallized in all isostructural with the corresponding paramagnetic [CpNi(dithiolene)] complexes, but [CpCo(dmid)] (Y = CO), [CpCo(dddt)] (Y = -(CH2)2-) and [CpCo(F2pddt)] (Y = -CH2CF2CH2-) crystallized in non-isostructural with them. These molecules are associated with intermolecular short S?S contacts in the crystals. [CpCo(F2pddt)] did not show any remarkable S?S contacts but indicated interesting fluorine segregation and Cp?Cp face-to-face interactions. Redox potentials of [CpCo(dithiolene)] complexes were obtained with the cyclic voltammetry measurements and dimerized by electrochemical oxidations. Electronic absorption spectra of [CpCo(dithiolene)] complexes showed visible absorption in the range of 585-701 nm as lowest energy wavelengths (? = 9800-11,800 M−1 cm−1) in solutions, and they were higher energy than those of [CpNi(dithiolene)] complexes (near-IR). 相似文献
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36.
Naoyuki Miyasaka Yoshihiro Doi Yukio Hinatsu 《Journal of solid state chemistry》2009,182(8):2104-2110
Synthesis, structures, and magnetic properties of ternary rare earth oxides ALnO2 (A=Cu or Ag; Ln=rare earths) have been investigated. CuLnO2 (Ln=La, Pr, Nd, Sm, Eu) were synthesized by the direct solid state reaction of Cu2O and Ln2O3, and AgLnO2 (Ln=Tm, Yb, Lu) were obtained by the cation-exchange reaction of NaLnO2 and AgNO3 in a KNO3 flux. These compounds crystallized in the delafossite-type structure with the rhombohedral 3R type (space group: R-3m). Magnetic susceptibility measurements showed that these compounds are paramagnetic down to 1.8 K. Specific heat measurements down to 0.4 K indicated that CuNdO2 ordered antiferromagnetically at 0.8 K. 相似文献
37.
Dr. Kei Kitamura Dr. Naoyuki Shimada Dr. Craig Stewart Dr. Abdurrahman C. Atesin Prof. Tülay A. Ateşin Prof. Dr. Marcus A. Tius 《Angewandte Chemie (International ed. in English)》2015,54(21):6288-6291
A Pd0‐catalyzed asymmetric Nazarov‐type cyclization is described. The optimized ligand for the reaction incorporates a weakly coordinating pyridine ring into a TADDOL‐derived phosphoramidite (TADDOL=α,α,α,α‐tetraaryl‐1,3‐dioxolane‐4,5‐dimethanol). The reaction leads to the formation of cyclopentenones as single diastereoisomers that incorporate two contiguous asymmetric centers, one tertiary and one an all‐carbon‐atom quaternary stereocenter, in high yield and optical purity. It is noteworthy that the reaction does not require that substrates should be activated by aryl substituents. 相似文献
38.
Kajitani T Onouchi H Sakurai S Nagai K Okoshi K Onitsuka K Yashima E 《Journal of the American Chemical Society》2011,133(24):9156-9159
We report a unique macromolecule consisting of a rodlike helical polyisocyanide backbone with a narrow molecular weight distribution and rigid mesogenic chiral pendants linked via a flexible spacer that exhibits lyotropic nematic and latticelike new smectic (lat-Sm) liquid crystal phases at different concentrations. The unprecedented lat-Sm phase is associated with the smectic ordering of both the stiff polymer backbone and the rigid-rod side groups. A detailed investigation of the films using X-ray scattering and atomic force microscopy revealed a novel tilted smectic layer structure of the polymer backbone aligned perpendicular to the smectic layer of the mesogenic pendants, which arrange in an antiparallel overlapping interdigitated manner. 相似文献
39.
The first example of enantioselective intermolecular cycloaddition of carbonyl ylides with indoles is described. The cycloaddition of five- and six-membered carbonyl ylides derived from diazodiketoesters with N-methylindoles under catalysis by dirhodium(II) tetrakis[N-tetrachlorophthaloyl-(S)-tert-leucinate], Rh(2)(S-TCPTTL)(4), gave cycloadducts in high yields and with high levels of enantioselectivity (up to 99% ee) as well as excellent exo diastereoselectivity. 相似文献
40.
Kimura T Koiso N Ishiwata K Kuwata S Ikariya T 《Journal of the American Chemical Society》2011,133(23):8880-8883
Hydrogenation and protonation of parent imido complexes have attracted much attention in relation to industrial and biological nitrogen fixation. The present study reports the structure and properties of the highly unsaturated diiridium parent imido complex [(Cp*Ir)(2)(μ(2)-H)(μ(2)-NH)](+) derived from deprotonation of a parent amido complex. Because of the Lewis acid-Br?nsted base bifunctional nature of the metal-NH bond, the parent imido complex promotes heterolysis of H(2) and deprotonative N-H cleavage of ammonia to afford the corresponding parent amido complexes under mild conditions. 相似文献