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91.
Teruaki Suzuki Minoru Suzuki Akio Furusaki Takaheshi Matsumoto Arata Kato Yoshihiko Imanaka Etsuro Kurosawa 《Tetrahedron letters》1985,26(10):1329-1332
Two new cyclic ethers consisting of squalene carbon skeleton have been isolated from the red alga L. obtusa. The absolute stereostructure of teurilene () was elucidated by x-ray crystallographic method, and the structure of thyrsiferyl 23-acetate () was established from the spectral and chemical evidence. 相似文献
92.
Yoshihiko Yamamoto Prof. Dr. Ken Yamashita Tomitaka Hotta Toru Hashimoto Makoto Kikuchi Dr. Hisao Nishiyama Prof. Dr. 《化学:亚洲杂志》2007,2(11):1388-1399
Spirocyclic C‐arylglycosides were synthesized from the appropriately protected δ‐gluconolactones. Addition of lithium acetylide followed by glycosylation with 3‐(trimethylsilyl)propargyl alcohol converted the δ‐gluconolactones into silylated diynes. After desilylation, subsequent ruthenium‐catalyzed cycloaddition of the resultant diynes with alkynes or chloroacetonitrile gave spirocyclic C‐arylglycosides in good yields and selectivity. This strategy was also extended to the synthesis of spirocyclic C‐arylribosides from the known γ‐ribonolactone derivative. Moreover, silver‐catalyzed iodination of the sugar diynes followed by ruthenium‐catalyzed cycloaddition with acetylene delivered spirocyclic C‐iodophenylglycosides and ‐ribosides, which were subjected to palladium‐catalyzed C? C bond‐forming reactions and copper‐catalyzed coupling with nitrogen heterocycles to lead to various derivatives. 相似文献
93.
Kotaro Hidea Yoshihiko Hayakawa Atsushi Ito Katsumi Kobayashi Takashi Ito 《Photochemistry and photobiology》1986,44(3):379-383
The wavelength dependence of the formation of two types of DNA damage, single-strand breaks and base changes, was investigated in the UV region from 150 nm to 254 nm using superhelical closed circular (form I) colicin El DNA with synchrotron radiation. Single-strand breaks were measured by agarose gel electrophoresis as a direct conversion of form I DNA to form II DNA (open circular). Base damages were defined as sensitive sites to a crude extract of endonuclease from Micrococcus luteus. They also were estimated using the same conversion, from form I to form II after the DNA was treated with endonuclease. The fluence-effect relationship could be fitted by a simple exponential function for both types of damage. Action spectra were constructed based on the reciprocal of the 37% fluence. The action spectrum for strand breaks increased rather monotonically over three decades from 254 nm to 150 nm in a logarithmic scale, while that for base damages showed a breaking point at 190 nm, being relatively flat above 190 nm. The characteristics of the action spectra are compared with the absorption spectra of the DNA and its main chain moiety calculated on the basis of data on calf thymus DNA and synthetic polynucleotides. Our main conclusions are (1) that the majority of single-strand breaks were induced by the absorption of photon in the sugar-phosphate group in the vacuum-UV region and (2) that the base changes were induced equally well by absorption in the vacuum-UV and in the far-UV region. 相似文献
94.
Takahashi T Tsai FY Li Y Wang H Kondo Y Yamanaka M Nakajima K Kotora M 《Journal of the American Chemical Society》2002,124(18):5059-5067
Selective preparation of pyridine derivatives from two different alkynes and a nitrile was achieved by a novel procedure in which an alkyne and a nitrile couple first to give an azazirconacyclopentadiene followed by reaction with the second alkyne in the presence of 1 equiv of NiCl(2)(PPh(3))(2). This procedure gives only single products of pyridine derivatives from two different symmetrical alkynes and a nitrile. Our novel procedure can be used even with two similar alkyl-substituted alkynes such as 3-hexyne and 4-octyne. Two possible pyridine isomers from 3-hexyne, 4-octyne, and acetonitrile could be completely and independently prepared as single products by this method. The origin of the selectivity comes from the addition order of two different alkynes. This method was applied for the formation of pyridones and iminopyridines using isocyanate and carbodiimide derivatives instead of nitriles, respectively. Reaction of an alkyne with Cp(2)ZrEt(2) and an isocyanate or a carbodiimide gives an azazirconacycle. Treatment of the azazirconacycle with the second alkyne in the presence of 1 equiv of NiCl(2)(PPh(3))(2) gave a pyridone or an iminopyridine derivative. The use of two different unsymmetrical alkynes afforded the pyridine with five different substituents when the first alkyne has a trialkylsilyl group and the second alkyne has a phenyl group as functional groups. On the other hand, azazirconacyclopentadienes reacted with propargyl bromide in the presence of CuCl with excellent regioselectivity to give tetrasubstituted pyridine derivatives as single products. With the assistance of the trialkylsilyl groups, pyridines with all different substituents including H were also prepared. 相似文献
95.
A general method for enlargement of carbocyclic rings by the so called zip reaction is given. The Michael adducts of 2-nitrocycloalkanones with 3-oxo-4-pentenoates in the presence of tetrabutylammonium fluoride give in high yield compounds with the ring enlarged by four C-atoms. By this method 7-, 8-, and 12-membered cycloalkanones were converted respectively to 11-, 12-, and 16-membered functionalized carbocycles (see Scheme 2 and 3). 相似文献
96.
Phosphorescence behavior of the series of compounds, (carbazole)-(CH2)n-(terephthalic acid methyl ester), which show intramolecular exciplex emission, has been studied in a rigid medium at 77 K. The phosphorescence of the carbazole moiety is enhanced by electron transfer fluorescence quenching of the carbazole residue in accord with the degree of quenching. 相似文献
97.
Suginome M Iwanami T Ohmori Y Matsumoto A Ito Y 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(10):2954-2965
Highly enantioenriched (E)-allylsilanes have been synthesized from optically active allylic alcohols on the basis of Pd-catalyzed intramolecular bis-silylation followed by highly stereospecific Si-O elimination reactions. The method involves three steps: 1) O-disilanylation of the allylic alcohols with chlorodisilanes, 2) intramolecular bis-silylation in the presence of a 1,1,3,3-tetramethylbutyl isocyanide/[Pd(acac)2] (acac = acetylacetonate) catalyst at 110 degrees C, and 3) treatment of the reaction mixture with organolithium reagents. The overall transformation proceeds with nearly complete conservation of the enantiopurity of the starting allyl alcohols by transposition of the C=C bond. For instance, (R)-(E)-3-decen-2-ol (99.6-99.7 % ee) produced (S)-(E)-4-(organosilyl)-2-decene of 98.8-99.4 % ee for a variety of silyl groups, including Me3Si, Me2PhSi, tBuMe2Si, Et3Si, and iPr3Si. In the bis-silylation step, the initially formed trans-1,2-oxasiletanes immediately dimerize to stereoselectively give 1,5-dioxa-2,6-disilacyclooctanes, which are isolated in high yield by carrying out the reaction at 70 degrees C. The eight-membered ring compounds undergo thermal extrusion of (E)-allylsilanes in high yield at 110 degrees C, along with formation of 1,3-dioxa-2,5-disilacyclohexane derivatives. These in turn undergo a Peterson-type elimination by treatment with nucleophiles such as BuLi and PhLi to give the (E)-allylsilanes. All of the steps involved in the sequence proceed with extremely high stereoselectivity and stereospecificity, leading to almost complete 1,3-chirality transfer through the overall transformation. The dimerization step, which forms diastereomeric intermediates, allows the synthesis of a highly enantioenriched allylsilane (99.4 % ee) from an optically active allylic alcohol with lower enantiopurity (79.2 % ee) by enrichment of enantiopurity. A general method for the determination of the enantiomeric excesses of (E)-allylsilanes is also described in detail. 相似文献
98.
(1,l-Dihydroperfluoroalkyl)phenyl- and --fluorophenyliodonium triflates and were synthesized by the reaction of l-bis(trifluoroacetoxy)iodo-1,l-dihydroperfluoroalkanes with triflic acid and benzene or fluorobenzene in 1,1,2-trichlorotrifluoroethane. The use of fluorosulfonic acid and sulfuric acid instead of triflic acid afforded (1,l-dihydroperfluoroalkyl) phenyliodonium fluorosulfonate and sulfate , respectively. Similarly, (1,1,ω-trihydroperfluoroalkyl)phenyliodonium triflate and 1,1,5,5-tetrahydroperfluoropentane-l,5-bisphenyliodonium triflate were synthesized. 相似文献
99.
Takashi Iizawa Tadatomi Nishikubo Midori Ichikawa Yoshihiko Sugawara Makoto Okawara 《Journal of polymer science. Part A, Polymer chemistry》1985,23(7):1893-1906
The reactions of poly(epichlorohydrin) (PECH) and poly(2-chloroethyl vinyl ether) (PCEVE) with various reagents were investigated using phase transfer catalyst (PTC) such as tetra-n-butylammonium bromide (TBAB), 18-crown-6 (CR6), and dicyclohexyl-18-crown-6 (DCHC) is a solid—liquid two-phase system. Although the reactions of these polymers hardly occurred without PTC in nonpolar solvents such as toluene and diglyme under mild conditions, the addition of PTC caused the reactions to proceed smoothly under the same conditions. In addition, the reactions of PECH and PCEVE with a strong base such as potassium hydroxide proceeded selectively through β-elimination reaction to produce the polymers with pendant vinyl groups. These results suggested this method is useful for the syntheses of functional polymers. On the other hand, it turned out that quaternary ammonium salts such as TBAB have higher catalytic activity than crown ethers such as CRG and DCHE in these reactions. Furthermore, the catalytic activity of quaternary ammonium salts was strongly influenced by their chain length and the structure of the polymers. 相似文献
100.
The catalytic intermolecular cyclotrimerization of alkynylboronates, propargyl alcohols, and terminal alkynes was accomplished by means of the ruthenium catalysis and the temporary tethering approach with the C-B-O linkage to give rise to highly substituted arylboronates with excellent selectivity. The resultant arylboronates were further converted to highly substituted biaryls via the Suzuki-Miyaura coupling with various aryl iodides using Pd2(dba)3/PCy3 as a catalyst precursor in aqueous toluene. As a consequence, the four-component coupling approach to highly substituted biaryls was successfully established by combining these two operations into a sequential one-pot process. 相似文献