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41.
Shindo M Yoshikawa T Itou Y Mori S Nishii T Shishido K 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,12(2):524-536
Ynolates were found to react with alpha-alkoxy-, alpha-siloxy-, and alpha-aryloxyketones at room temperature to afford tetrasubstituted olefins with high Z selectivity. Since the geometrical selectivity was determined in the ring opening of the beta-lactone enolate intermediates, the torquoselectivity was controlled by the ethereal oxygen atoms. From experimental and theoretical studies, the high Z selectivity is induced by orbital and steric interactions rather than by chelation. In a similar manner, alpha-dialkylamino ketones provided olefins with excellent Z selectivity. These products can be easily converted into multisubstituted butenolides and gamma-butyrolactams in good yield. 相似文献
42.
(+)-Biotin (1) was synthesized in 25% overall yield over 11 steps from L-cysteine. The contiguous asymmetric centers at C-3a and C-6a were formed through a novel and highly stereoselective Lewis base-catalyzed cyanosilylation of alpha-amino aldehyde 3 to provide anti-O-TMS-cyanohydrin 4 with high stereoselectivity and in high yield (anti/syn = 92:8, 96%). Treatment of 4 with a di-Grignard reagent, 1,4-bis(bromomagnesio)butane, followed by carbon dioxide, efficiently installed the 4-carboxybutyl chain at C-4 to give keto acid 5. The final cyclization to bicyclic compound 7b, a precursor to 1, was realized by a palladium-catalyzed intramolecular allylic amination of cis-allylic carbonate 6b that was elaborated from 5. 相似文献
43.
S Yokohama T Miwa S Aibara H Fujiwara H Matsumoto K Nakayama T Iwamoto M Mori R Moroi W Tsukada 《Chemical & pharmaceutical bulletin》1992,40(9):2391-2398
A series of 6-alkyl- or 6-(cycloalkylalkyl)-[1,3,4]thiadiazolo[3,2- a]-1,2,3-triazolo[4,5-d]pyrimidin-9(3H)-ones 1b--o was synthesized from the corresponding 1,3,4-thiadiazol-5-amines 3b--o and the antiallergic activities of the products were evaluated. Among the compounds 6-(2-cyclohexylethyl)- [1,3,4]thiadiazolo[3,2-a]-1,2,3-triazolo[4,5-d]pyrimidin-9(3H)-one 1h, whose X-ray crystallographic stereostructure is shown, was found to be a promising new antiallergic agent, which has low toxicity and dual activity as a leukotriene D4 receptor antagonist and as an orally active mast cell stabilizer. 相似文献
44.
Yoshiyuki Goh Takao Iijima Masao Tomoi 《Journal of polymer science. Part A, Polymer chemistry》2002,40(15):2702-2716
Novel quaternary ammonium bis(2‐oxybenzoyloxy)borate salts ( 1a – 1c ) or quaternary ammonium bis(1,2‐benzenedioxy)borate salts ( 2a and 2b ) with tetra‐n‐butylammonium (TBA+), tetra‐n‐octylammonium (TOA+), or bis(triphenylphosphoranylidene)ammonium (PNP+) cations were synthesized as latent catalysts of epoxy/phenol–novolac resins by the complexation between boric acid and salicylic acid or catechol, followed by neutralization with quaternary ammonium hydroxide. Polyaddition reactions of diglycidyl ether of bisphenol A (DGEBA) and 4,4′‐bisphenol F (44BPF) or bisphenol F (BPF‐D) with the ammonium borates were investigated as model reactions of epoxy/phenol–novolac resin systems with respect to the thermal latency and storage stability of the catalyst. The polyaddition of DGEBA/44BPF with 1a – 1c in diglyme at 150 °C for 6 h proceeded up to 85–96% conversions and gave polymers with number‐average molecular weights of 4180–10,500, whereas the polyaddition at 80 °C for 6 h gave less than 8% conversions. However, the polyaddition with 2a containing TBA+ cation proceeded to only a 32% conversion at 150 °C for 6 h in diglyme and to a 64% conversion even at 180 °C for 6 h in triglyme and only gave low molecular weight oligomers, and no reaction proceeded in the polyaddition at 80 °C. However, polyaddition with 2b containing PNP+ cation proceeded up to a 96% conversion at 150 °C for 6 h in diglyme and gave a higher molecular weight polymer with a number‐average molecular weight of 8050, whereas the polyaddition at 80 °C for 6 h gave only a 5% conversion. The catalytic activity of ammonium borates 1a – 1c and 2a and 2b depended on the borate anion structure: 1a and 1c with bis(2‐oxybenzoyloxy)borate anion revealed higher activity than 2a and 2b with bis(1,2‐benzenedioxy)borate anion, respectively. In comparison with tetra‐n‐butylammonium bromide (TBAB) as a conventional ammonium salt or tetra‐n‐butylammonium tetrakis(benzoyloxy)borate (TBA‐TBB), 1a – 1c and 2b revealed better thermal latency. The catalytic activity of ammonium borates also depended on the bulkiness of the ammonium cation, and the order of activity was 1c (PNP+) > 1b (TOA+) ≧ 1a (TBA+) and 2b (PNP+) > 2a (TBA+). The storage stability of DGEBA/BPF‐D with the ammonium borate catalysts 1a – 1c and 2a and 2b in bulk at 40 °C was much better than that with TBAB and TBA‐TBB. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2702–2716, 2002 相似文献
45.
Chiaki Azuma Takao Mitsuboshi Kohei Sanui Naoya Ogata 《Journal of polymer science. Part A, Polymer chemistry》1980,18(3):781-797
cis-1,4-Polybutadiene and polypentenamer having pendant functional groups such as formyl, aldoxime, hydroxymethyl, or cinnamoyloxymethyl groups have been prepared, and some of their properties were investigated in terms of structural effect on physical properties of these polymers. cis-1, 4-Polybutadiene and polypentenamer having a different content of formyl group were prepared by the hydroformylation reaction with rhodium catalyst under mild conditions. The pendant formyl group was reduced to a hydroxymethyl group by using various reducing agents such as sodium borohydride or sodium trimethoxyborohydride which were effective to avoid a crosslinking reaction among the formyl groups. Glass transition temperature of polypentenamer having hydroxymethyl groups increased with increasing the content of the hydroxymethyl groups in the polymer. Cinnamoyl group was introduced into the polypentenamer having hydroxymethyl groups by reacting with cinnamoyl chloride so as to prepare a photosensitive rubber. The relationships between the photosensitivity of the cinnamoylated polypentenamer and the mobility of polymer main chains have been elucidated. A linear relationship between the photodimerization rate constant and the difference between ultraviolet (UV) irradiation temperature and the glass transition temperature of the polymer was found. It has become apparent that the photosensitivity of cinnamoylated polypentenamer can be estimated by the glass transition temperature of the original polymer, UV irradiation temperature, activation energy of the dimerization, and γ, which is a coefficient of the relationship between the photosensitive group concentration and the glass transition temperature of the polymer. 相似文献
46.
The structures of two new bitter triterpenes, ganoderic acid A and B. isolated from a mushroom Ganoderma lucidum (FR.) Karst. (Polyporaceae) were determined as 1 and 2 on the basis of spectral data. Ganoderic acid A is a novel highly oxidized triterpene bearing a boat-shaped A-ring of lanostane. 相似文献
47.
(R)-(+)-Seudenol (3-methylcyclohex-2-en-1-ol) and its antipode were synthesized from optically active forms of 3-iodocyclohex-2-en-1-ol by treatment with Me2CuLi. Their absolute configurations were determined by converting (+)-3-iodocyclohex-2-en-1-ol to the known (R)-(+)-cyclohex-2-en-1-ol. 相似文献
48.
Mori A Kawashima J Shimada T Suguro M Hirabayashi K Nishihara Y 《Organic letters》2000,2(19):2935-2937
Palladium-catalyzed reaction of aryl and alkenyl halides with terminal alkynes in the presence of silver(I) oxide as an activator furnishes various arylated or alkenylated alkynes in good to excellent yields. The similar coupling reaction is also found to proceed using tetrabutylammonium fluoride (TBAF) or tetrabutylammonium hydroxide (TBAOH) as an activator. 相似文献
49.
Y Fukuyama M Kodama I Miura Z Kinzyo M Kido H Mori Y Nakayama M Takahashi 《Chemical & pharmaceutical bulletin》1989,37(2):349-353
Eckol (1), a novel phlorotannin with a dibenzo-1,4-dioxin skeleton, has been isolated from the brown alga Ecklonia kurome Okamura as a potent and specific anti-plasmin inhibitor. Its structure has been elucidated based on the spectral data, in particular, by means of negative nuclear Overhauser effect (NOE), and finally established as 1-(3,5-dihydroxyphenoxy)-2,4,7,9-tetrahydroxydibenzo-1,4-dio xin by X-ray analysis. Some partially methoxylated derivatives of eckol were prepared by methylation with diazomethane and also by selective dimethylation of eckol permethylate (1b) to establish the structural requirements for inhibitory activities on alpha 2-macroglobulin and alpha 2-plasmin inhibitor, the main plasmin inhibitors in plasma. 相似文献
50.
The long-range correction (LC) scheme for the exchange functional of density-functional theory (DFT) was combined with the coupled-perturbed Kohn-Sham (CPKS) method to calculate nonlinear optical response properties. By using this LC-CPKS method, we calculated the hyperpolarizabilities of typical molecules and the dipole moments, polarizabilities, and hyperpolarizabilities of push-pull pi-conjugated systems: p-nitroaniline, 4-amino-4'-nitrostilbene, and alpha,omega-nitroaminopolyenes. It was found that the LC scheme clearly improved the calculation of these optical properties for all of these systems, which have been significantly overestimated by conventional DFTs. We therefore concluded that the long-range exchange interaction played an important role in calculating the optical properties using the DFT formalism. 相似文献