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101.
Diversity-oriented organic synthesis (DOS) is a key concept for construction of skeletally diverse small molecule libraries to discover drug-like small molecules. Here, we describe a DOS class to transform a complex 7-oxanorbornene skeleton, which is readily accessible by a tandem Ugi/Diels-Alder reaction, into two heterotricycle skeletons selectively by using tandem ROM/CM/RCM reaction. In the present study, the mode of cyclization is pre-encoded by building blocks used in the complexity-generating tandem Ugi/Diels-Alder reaction. Since variable alkenes can be used in the CM reaction, our approach can be extended to construct both skeleton- and appendage-diverse small molecule libraries. 相似文献
102.
Jun Haginaka Chikako Seyama Tokiko Murashima
Hiroya Fujima
Hiroo Wada 《Journal of chromatography. A》1994,660(1-2):275-281The influence of the physical properties of base silica materials and spacer length on chiral separation of enantiomers on ovomucoid (OVM)-bonded materials was investigated. With regard to the pore size of the base silica materials, the 300-Å materials gave higher enantioselectivity, than the 120-Å materials, despite the smaller amounts of bonded OVM proteins. However, higher resolution was obtained with the latter materials. With regard to the spacer length, aminopropyl (AP)-, aminobutyl-, N-(4-aminobutyl)-3-aminopropyl- and N-(6-aminohexyl)-3-aminopropyl-silica gels were activated by N,N′-di-succinimidyl carbonate (DSC) and the proteins were bound. The first two materials showed excellent chiral resolution properties for the solutes tested, and the AP materials gave higher enantioselectivity and resolution. On the other hand, only oxprenolol enantiomers were slightly resolved on the last two materials. Also, AP-silica gels activated by DSC were compared with glycerylpropyl (GP)-silica gels activated by 1,1′-carbonyldiimidazole. The former materials gave higher resolution for acidic and basic solutes despite the lower enantioselectivity, whereas for the unchanged hexobarbital the latter materials gave higher enantioselectivity and almost equal resolution. The above results reveal that the 120-Å base silica gels are more suitable than the 300- Å base silica gels for obtaining larger amounts of bonded OVM proteins and that a less hydrophobic spacer such as an AP group and a hydrophilic spacer such as a GP group are suitable. 相似文献
103.
Bando T Narita A Sasaki S Sugiyama H 《Journal of the American Chemical Society》2005,127(40):13890-13895
We examined DNA alkylation by pyrrole (Py)-imidazole (Im) hairpin polyamides, which possess 1,2,9,9a-tetrahydrocyclopropa[1,2-c]benz[1,2-e]indol-4-one (CBI) or cyclopropapyrroloindole (CPI) as DNA alkylating moieties. High-resolution denaturing gel electrophoresis revealed that alkylation by CBI conjugates 2 and 4 occurred specifically at adenines (A) in matched sequences, whereas CPI conjugates 1 and 3 alkylated both A and guanines (G) in matched sequences. The origin of the different reactivity of CBI and CPI conjugates is discussed in relation to the electrophilicity of the cyclopropane moiety. The high selectivity of the CBI conjugate gives additional sequence specificity relative to CPI conjugates that would be useful for the biological applications. 相似文献
104.
Shimizu H Tada N Ikawa R Kume T Sasaki S 《The journal of physical chemistry. B》2005,109(47):22285-22289
Visual observations through a microscope and in situ Raman measurements have been made for single crystalline ethylene hydrate (EH) and binary methane-ethylene hydrate (MEH) at pressures up to 3.7 GPa and room temperature. Both hydrates showed pressure-induced phase transitions at 1.6, 2.0, and 3.0 GPa for EH and at 1.7, 2.1, and 3.3 GPa for MEH. The cubic sI phase of EH and MEH remains stable up to 1.6 and 1.7 GPa, respectively, which are more widely ranging values than the values for the methane hydrate sI phase. In this sI phase of binary MEH, the cage occupancies by methane and ethylene molecules are investigated from Raman spectra. Above P = 3.0 GPa for EH and 3.3 GPa for MEH, they decomposed by associating with the formation of the polyethylene. 相似文献
105.
Yasuo Shimano Shoichi Sasaki 《Journal of polymer science. Part A, Polymer chemistry》1983,21(5):1331-1345
Reaction of sulfinylaminobenzoyl chlorides with lead thiocyanate gave sulfinylaminobenzoyl isothiocyanates (SBIs), from which were derived aminobenzoyl isothiocyanate hydrochlorides (ABIHs). AB polyacylthioureas (PATUs) with inherent viscosities of up to 0.28 dL/g were obtained by treating the SBI with an equivalent of water in N-methyl-2-pyrrolidone (NMP). Low-temperature solution polyaddition of the ABIH afforded AB PATU with inherent viscosities of up to 0.66 dL/g, which were further increased to as high as 0.75 dL/g by adding lithium bases to the polymerization mixtures. Polyaddition of isophthaloyl diisothiocyanate with intermediate diamines formed by hydrolyzing the adducts of SBI and aromatic diamines afforded copolyacylthioureas with inherent viscosities of up to 1.15dL/g. The copolymers were generally soluble in NMP, whereas solubilities of the AB PATU in analogous solvents were relatively low. Thermogravimetric analyses in both air and nitrogen exhibited weight losses of 5% at 204–236°C for AB PATU and at 170–192°C for the copolymers. 相似文献
106.
Takakazu Yamamoto Abla Mahmut Masahiro Abe Shin‐Ichi Kuroda Tatsuya Imase Shintaro Sasaki 《Journal of Polymer Science.Polymer Physics》2005,43(16):2219-2224
An alternating copolymer, Copoly‐1 , of thiophene and N‐(phenylethynyl)pyrrole was prepared by palladium‐catalyzed polycondensation. Powder X‐ray diffraction (XRD) analysis indicated that Copoly‐1 formed a stacked packing structure with doubly‐running polymer main chains. Optical data support the molecular and packing structures of Copoly‐1 . © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2219–2224, 2005 相似文献
107.
Here, we report a diversity-oriented synthetic approach toward skeletally diverse, cyclized peptidomimetics with diverse appendages. Starting from α-(N-acylamino)amides with various appendages, 12 to 16-membered lactams with defined olefin geometry were synthesized by a common synthetic sequence. We also synthesized the macrocycle in a liquid phase directed toward a construction of the peptidomimetics library. 相似文献
108.
Hisanobu Ogoshi Kazurni Saita Ken-ichi Sakurai Takamichi Watanabe Hiroo Toi Yasuhiro Aoyama 《Tetrahedron letters》1986,27(52):6365-6368
Described is the preparation of chiral octaethylporphyrin derivatives having two 2-substituted naphthyl groups in a trans orientation at the 5- and 15-meso positions and formyl or hydroxymethyl or alkoxymethyl group derived therefrom at the 10-meso position. One of the derivatives has been successfully resolved into enantiomers by means of HPLC. 相似文献
109.
110.
Computer-aided structure elucidation methodology is discussed. Major processes involved in computer-aided structure elucidation systems are partial-structure elucidation, structure generation, and structure examination. For the three representative systems CONGEN, CASE, and CHEMICS, these processes are examined. There are four necessary conditions for automated chemical structure elucidation systems: reliability, width of application, ease of modification and portability. 相似文献