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61.
The transient absorption properties of several commercially available TiO2 photocatalysts were investigated by femtosecond diffuse-reflectance spectroscopy. Using femtosecond diffuse-reflectance spectroscopy, the quantities and rates of the initial trapping processes of holes and electrons generated by the photoexcitation of TiO2 photocatalysts were investigated. It was found that the total amounts of trapped electrons for the pure-anatase and pure-rutile TiO2 became smaller with increasing particle size, but increased again when the particles’ diameters were larger than 50 nm. The anatase–rutile mixed TiO2 photocatalysts were found to have smaller amounts of trapped electrons compared with pure-anatase and pure-rutile TiO2 photocatalysts. The lifetimes of trapped holes of various TiO2 photocatalysts were also investigated, and it was found that the lifetimes were proportional to the anatase–rutile mixed ratios. 相似文献
62.
Regio- and diastereoselective reaction of oxygen and sulfur substituted allylic carbanions with aldehydes is described. Either threo or erythro isomer can be obtained predominantly or exclusively by merely choosing an additive. 相似文献
63.
Nakamura I Mizushima Y Gridnev ID Yamamoto Y 《Journal of the American Chemical Society》2005,127(27):9844-9847
A new catalytic cyclization of o-alkynylbenzaldehyde acetals 1 to the functionalized indenes 2 was found to be strictly controlled by the number of triphenylphosphine ligands on the Pd catalyst. Only complexes with three available coordination sites on Pd catalyze this reaction. Mechanistic study suggests that pi-coordination of Pd to the benzene ring is a key step controlled by the number of vacant coordination sites. 相似文献
64.
Reactions of methyl 2-cyano-3,3-bis(methylthio)acrylate ( 1a ) with carboxamides 2a-g in the presence of sodium hydride in a mixture of benzene and N,N-dimethylacetamide took place displacement with the methylthio group to give the corresponding methyl 3-N-acylamino-2-cyano-3-(methylthio)acrylates 3a-g which were readily converted to the corresponding pyrimidine derivatives at reflux in methanol in good yields. Reactions of 2-cyano-3,3-bis(methylthio)acrylonitrile ( 1b ) with the carboxamides 2a-f gave directly pyrimidine-5-carbonitrile derivatives 7a-f . Ketene dithioacetals 1a,b smoothly reacted with thioamide 2g or urea 2h,i to give the expected pyrimidine derivatives 9,10a,b . Polyfunctionalized pyrimidines, thus obtained, were also used for the synthesis of fused pyrimidine derivatives. 相似文献
65.
Miyagawa T Nagai K Yamada A Sugihara Y Fukuda T Fukuda T Uchida R Tomoda H Omura S Nagamitsu T 《Organic letters》2011,13(5):1158-1161
The first total synthesis of citridone A has been achieved through regioselective intramolecular iodocyclization and regio- and stereoselective Pd(0)-catalyzed coupling as key reactions. 相似文献
66.
Ueda M Makino A Imai T Sugiyama J Kimura S 《Chemical communications (Cambridge, England)》2011,47(11):3204-3206
Two types of peptide nanotubes, one is prepared from an amphiphilic peptide having a right-handed helix segment and the other from that having a left-handed helix segment, are shown to transform the morphology into a vesicle by membrane fusion due to stereo-complex formation between these helical segments. 相似文献
67.
Highly enantioselective gem-chlorofluorination of active methylene compounds was carried out by using a copper(II) complex of a chiral spiro pyridyl monooxazoline ligand. This reaction yielded α-chloro-α-fluoro-β-keto esters and α-chloro-α-fluoro-β-keto phosphonates with up to 92% ee. The resulting dihalo β-keto ester was converted into various α-fluoro-α-heteroatom-substituted carbonyl compounds via nucleophilic substitution without loss of optical purity. A fully protected β-amino acid with a gem-chlorofluoromethylene function was also synthesized. 相似文献
68.
Sano S Okubo Y Handa A Nakao M Kitaike S Nagao Y Kakegawa H 《Chemical & pharmaceutical bulletin》2011,59(7):885-888
Isoliquiritigenin [ILG, (E)-1] was readily prepared via the Horner-Wadsworth-Emmons reactions using β-ketophosphonates 5a, b. An improved protocol for the synthesis of (E)-1 via the Claisen-Schmidt condensation was also presented. 相似文献
69.
Yoshinori Tominaga Yoshihide Shiroshita Tomohiko Kurokawa Hiromi Gotou Yoshiro Matsuda Akira Hosomi 《Journal of heterocyclic chemistry》1989,26(2):477-487
The reaction of 1-ethoxycarbonylmethylpyridinium bromides 5a-k with nitro ketene dithioacetal, 1,1-bis-(methylthio)-2-nitroethylene ( 2 ), in the presence of triethylamine in ethanol gave the desired ethyl 2-methyl-thioindolizine-3-carboxylates 3a-k in good yields, along with ethyl 2-methylthio-1-nitroindolizine-3-carboxyl-ates 4a-d . Deesterification of 3 using sodium hydroxide in methanol followed by treatment with polyphosphoric acid gave the corresponding 2-methylthioindolizines 5a-d in good yields. The desulfurization of 5 with Raney-nickel in ethanol occurs smoothly to give the 1,2,3-unsubstituted indolizines 6a-c (a , parent indolizine; b , 8-methylindolzine; c , 6,8-dimethylindolizine). Similarly, pyrrolo[2,1-a]isoquinoline ( 19 ) was also synthesized. These indolizine and pyrrolo[1,2-a]isoquinoline derivatives were allowed to react with dimethyl acetylene to give the corresponding cycl[3.2.2]azine and benzo[g]cycl[3.2.2]azine derivatives in good results. 相似文献
70.
Motoyama T Shimazaki Y Yajima T Nakabayashi Y Naruta Y Yamauchi O 《Journal of the American Chemical Society》2004,126(23):7378-7385
The Pd(II) complexes of new 2N1O-donor ligands containing a pendent indole, 3-[N-2-pyridylmethyl-N-2-hydroxy-3,5-di(tert-butyl)benzylamino]ethylindole (Htbu-iepp), 1-methyl-3-[N-2-pyridylmethyl-N-2-hydroxy-3,5-di(tert-butyl)benzylamino]ethylindole (Htbu-miepp), 3-[N-2-pyridylmethyl-N-2-hydroxy-3,5-di(tert-butyl)benzylamino]methylindole (Htbu-impp), and 3-(N-2-pyridylmethyl-N-4-hydroxybenzylamino)ethylindole (Hp-iepp) (H denotes a dissociable proton), were synthesized, and the structures of [Pd(tbu-iepp)Cl] (1a), [Pd(tbu-iepp-c)Cl] (1b), [Pd(tbu-miepp)Cl] (3), and [Pd(p-iepp-c)Cl] (4) (tbu-iepp-c and p-iepp-c denote tbu-iepp and p-iepp bound to Pd(II) through a carbon atom, respectively) were determined by X-ray analysis. Complexes 1a prepared in CH(2)Cl(2)/CH(3)CN and 3 prepared in CH(3)CN have a pyridine nitrogen, an amine nitrogen, a phenolate oxygen, and a chloride ion in the coordination plane. Complex 1b prepared in CH(3)CN has the same composition as 1a and was revealed to have the C2 atom of the indole ring bound to Pd(II) with the Pd(II)-C2 distance of 1.973(2) A. The same Pd(II)-indole C2 bonding was revealed for 4. Interconversion between 1a and 1b was observed for their solutions, the equilibrium being dependent on the solvent used. Reaction of 1b and 4 with 1 equiv of Ce(IV) in DMF gave the corresponding one-electron-oxidized species, which exhibited an ESR signal at g = 2.004 and an absorption peak at approximately 550 nm, indicating the formation of the Pd(II)-indole pi-cation radical species. The half-life, t(1/2), of the indole radical species at room temperature was calculated to be 20 s (k(obs) = 3.5 x 10(-)(2) s(-)(1)) for 1b. The cyclic voltammogram for 1b in DMF gave two irreversible oxidation peaks at E(pa) = 0.68 and 0.80 V (vs Ag/AgCl), which were ascribed to the oxidation processes of the coordinated indole and phenolate moieties, respectively. 相似文献