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11.
[reaction: see text] Base-promoted cyclocondensation of C-chloro oximes with cyclic 1,3-diketones affords functionalized isoxazoles in good yield and under convenient reaction conditions. This process enables the synthesis of highly substituted products with notable functional group tolerance. The products obtained are directly converted to a variety of polyketide-derived polycyclic structures including xanthenes, anthracenes, and benzophenones. 相似文献
12.
Tsutomu Konno Jungha Chae Tomoo Tanaka Takashi Ishihara Hiroki Yamanaka 《Journal of fluorine chemistry》2006,127(1):36-43
Hydroalumination, hydrocupration, and hydroboration reactions of various fluorine-containing alkynes were investigated. The alkyne reacted smoothly with 2.0 equiv. of Red-Al at −78 °C to give the hydroaluminated adduct in a highly regio- and stereoselective manner, which was treated with iodine, the corresponding vinyliodide being produced in moderate yield. Hydrocupration of the alkynes also took place, but the resulting vinylmetal reacted with various electrophiles sluggishly. In sharp contrast, the reaction with dicyclohexylborane proceeded smoothly to afford the cis-addition products preferentially, which were subjected to Suzuki-Miyaura cross-coupling reaction, leading to trisubstituted alkenes in high yields. 相似文献
13.
Hideaki Hioki Yumiko Ohnishi Miwa Kubo Emi Nashimoto Yukinori Kinoshita Miho Samejima Mitsuaki Kodama 《Tetrahedron letters》2004,45(3):561-564
A fluorescence-labeled calix[4]arene library substituted with peptides at the upper rim was synthesized. Screening of the library for binding a dye-labeled oligopeptide indicated that some peptidocalix[4]arenes selectively bind the oligopeptide. The chemosensitivity of the library members for a target peptide was also investigated. 相似文献
14.
Ishii K Itoya H Miwa H Fujitsuka M Ito O Kobayashi N 《The journal of physical chemistry. A》2005,109(26):5781-5787
We have investigated the excited-state properties and singlet oxygen ((1)Delta(g)) generation mechanism in phthalocyanines (4M; M = H(2), Mg, or Zn) and in low-symmetry metal-free, magnesium, and zinc tetraazaporphyrins (TAPs), that is, monobenzo-substituted (1M), adjacently dibenzo-substituted (2AdM), oppositely dibenzo-substituted (2OpM), and tribenzo-substituted (3M) TAP derivatives, whose pi conjugated systems were altered by fusing benzo rings. The S(1)(x) and S(1)(y) states (these lowest excited singlet states are degenerate in D(4)(h) symmetry) split in the low-symmetry TAP derivatives. The excited-state energies were quantitatively determined from the electronic absorption spectra. The lowest excited triplet (T(1)(x)) energies were also determined from phosphorescence spectra, while the second lowest excited triplet (T(1)(y)) states were evaluated by using the energy splitting between the T(1)(x) and T(1)(y) states previously reported (Miwa, H.; Ishii, K.; Kobayashi, N. Chem. Eur. J. 2004, 10, 4422-4435). The singlet oxygen quantum yields (Phi(Delta)) are strongly dependent on the pi conjugated system. In particular, while the Phi(Delta) value of 2AdH(2) is smallest in our system, that of 2OpH(2), an isomer of 2AdH(2), is larger than that of 4Zn, in contrast to the heavy atom effect. The relationship between the molecular structure and Phi(Delta) values can be transformed into a relationship between the S(1)(x) --> T(1)(y) intersystem crossing rate constant (k(ISC)) and the energy difference between the S(1)(x) and T(1)(y) states (DeltaE(S)(x)(T)(y)). In each of the Zn, Mg, and metal-free compounds, the Phi(Delta)/tau(F) values (tau(F): fluorescence lifetime), which are related to the k(ISC) values, are proportional to exp(-DeltaE(S)(x)(T)(y)), indicating that singlet oxygen ((1)Delta(g)) is produced via the T(1)(y) state and that the S(1)(x) --> T(1)(y) ISC process follows the energy-gap law. From the viewpoint of photodynamic therapy, our methodology, where the Phi(Delta) value can be controlled by changing the symmetry of pi conjugated systems without heavy elements, appears useful for preparing novel photosensitizers. 相似文献
15.
M. Kashiwara T. Miwa J. -U. H. Petersen C. M. Yung 《Selecta Mathematica, New Series》1996,2(3):415-499
In [S], [KMS] the semi-infinite wedge construction of level 1U
q
(A
n
(1)
) Fock spaces and their decomposition into the tensor product of an irreducibleU
q
(A
n
(1)
)-module and a bosonic Fock space were given. Here a general scheme for the wedge construction ofq-deformed Fock spaces using the theory of perfect crystals is presented.LetU
q
(g) be a quantum affine algebra. LetV be a finite-dimensionalU
q
(g)-module with a perfect crystal base of levell. LetV
aff V [z,z
–1] be the affinization ofV, with crystal base (L
aff,B
aff). The wedge spaceV
aff V
aff is defined as the quotient ofV
aff V
aff by the subspace generated by the action ofU
q
(g) [z
a
z
b
+z
b
z
a
]a,b onv v (v an extremal vector). The wedge space r
V
aff (r ) is defined similarly. Normally ordered wedges are defined by using the energy functionH :B
aff B
aff . Under certain assumptions, it is proved that normally ordered wedges form a base of r
V
aff.Aq-deformed Fock space is defined as the inductive limit of r
V
aff asr , taken along the semi-infinite wedge associated to a ground state sequence. It is proved that normally ordered wedges form a base of the Fock space and that the Fock space has the structure of an integrableU
q
(g)-module. An action of the bosons, which commute with theU
q
(g)-action, is given on the Fock space. It induces the decomposition of theq-deformed Fock space into the tensor product of an irreducibleU
q
(g)-module and a bosonic Fock space.As examples, Fock spaces for typesA
2n
(2)
,B
n
(1)
,A
2n
–1/(2)
,D
n
(1)
andD
n
+1/(2)
at level 1 andA
1
(1)
at levelk are constructed. The commutation relations of the bosons in each of these cases are calculated, using two point functions of vertex operators. 相似文献
16.
17.
[structure: see text] Thioxo peptide analogues of the alpha-helical peptide GCN4-p1 were synthesized and evaluated for helicity and oligomeric state. Sedimentation equilibrium and CD measurements indicate that the thioxo peptides fold into parallel alpha-helical coiled coil structures essentially identical to the native structure. This work marks the first incorporation of a thioamide linkage into the backbone of an alpha-helix and demonstrates that a thioamide linkage is compatible with positions within the helix as well as near the C-terminus. 相似文献
18.
Okada Y Yokozawa M Akiba M Oishi K O-kawa K Akeboshi T Kawamura Y Inokuma S Nakamura Y Nishimura J 《Organic & biomolecular chemistry》2003,1(14):2506-2511
A variety of aromatic compounds with both activating and deactivating substituents were brominated with sodium monobromoisocyanurate (SMBI) 1, diethyl ether, diethyl ether-methanesulfonic acid, trifluoroacetic acid, or sulfuric acid were employed as solvents. Thus nitrobenzene was conveniently brominated in sulfuric acid, benzene was readily monobrominated in diethyl ether-methanesulfonic acid, and phenol was selectively brominated at the ortho position under mild conditions in refluxing diethyl ether. With substituents that are easily protonated, trifluoroacetic acid may be employed as solvent in the reaction with 1, in contrast NBS was ineffective in trifluoroacetic acid. This renders 1 a superior reagent relative to NBS. In addition to aromatics, alkenes, ketones and esters were also brominated with 1. Diethyl malonate was brominated with 1 and then subjected to a Bingel reaction with NaH to afford the desired methanofullerene in reasonable yield. 相似文献
19.
Miwa Kubo 《Tetrahedron letters》2006,47(12):1927-1931
We synthesized a peptidocalix[4]arene library consisting of 1000 members that was suitable for peptide recognition in aqueous media. Some peptidocalix[4]arenes in the library were host molecules for guest peptides. Electrostatic interaction between the host and guest molecules was the most important factor for binding in aqueous media. 相似文献
20.
From the ethyl acetate soluble fraction of twigs of Magnolia denudata (Magnoliaceae), seven new neolignan derivatives, 1-7, were isolated along with eighteen known lignan and neolignan derivatives, 8-25. The structures of the new neolignans were elucidated by means of spectral methods, especially by 1H-NMR and 13C-NMR spectra, and two dimensional NMR methods such as 1H-detected heteronuculear multiple bond connectivity1 (HMBC), 1H-detected multiple quantum coherence (HMQC) and 1H-1H-correlation spectroscopy (COSY). Compounds 1-4 have novel structures possessing a 6-oxabicyclo[3.2.2]nonane skeleton and compounds 5-8 also have novel structures possessing a bicyclo[3.2.1]octane skeleton. The anti-platelet-activating factor (PAF) activity of these compounds was tested by measurement of inhibition activity against acetyl transferase to lyso-PAF. 相似文献