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31.
32.
Iwasaki Y Matsui R Suzuki T Nakazaki A Kobayashi S 《Chemical & pharmaceutical bulletin》2011,59(4):522-524
We have developed a high-yielding and stereoselective vinylogous Mukaiyama aldol reaction (VMAR) of α-haloenals. Contrary to the simple α,β-unsaturated aldehyde, α-haloenals were found to be reactive affording the corresponding VMAR adducts in excellent yields. Some transformations of VMAR adducts by Pd-mediated cross-coupling were also examined in order to demonstrate the synthetic utility of VMAR of α-haloenals. 相似文献
33.
Chlorination of the N-oxides of furo[2,3-b]- 1a , -[2,3-c]- 1b and -[3,2-c]pyridine 1c with phosphorus oxychloride afforded compounds substituted normally at the α- or λ-position to the ring nitrogen, 2a, 2′a, 2b, 2c, 2′c and 2′c , and in addition, in the case of 1b , compounds substituted on the furan ring, 2′b and 2″b . The structures of these compounds were confirmed from their ir, nmr and mass spectra. The major chlorinated products 2a, 2b and 2c were converted to methoxy- 5a, 5b and 5c , N-pyrrolidyl- 7a, 7b and 7c , and phenylthiofuropyridines 8a, 8b , and 8c . 相似文献
34.
Nobuo Tanaka Hironobu Iwasaki Takeshi Fukutome Ken Hosoya Takeo Araki 《Journal of separation science》1997,20(10):529-538
Pseudo-stationary phases for electrokinetic chromatography were prepared by the alkylation of starburst dendrimers (SBDs). The SBD-supported pseudo-stationary phase with dodecyl groups showed higher efficiency than short-akyl derivatives, and maintained the hydrophobic property inthe presence of methanol. The dodecyl-modified SBD provided wide migration time windows ar high methanol content to effect the separation of sixteen aromatic hydrocarbons, the priority pollutants designated by EPA, in 65% methanol. The selectivity of polymer-supported pseudo-stationary phase can be varied simply by changing the length of the alkyl groups. The dodecyl SBD showed relatively similar selectivity as sodium dodecyl culfate micelle, whereas short alkyl derivatives showed preference towards rigid and planar compounds based on the rigid and planar compounds based on the rigid polymer backbones. The selectivity of SBD-supported pseudo-stationary phases was dominated by the chain length of the alkyl groups, with the minor effect of the structure of the core and the generation of SBD where alkyl groups were attached. 相似文献
35.
This study presents the novel concept of a transformable protecting group, which changes its properties through structural transformation. Based on this concept, we developed a 2-(2-ethynylphenyl)-2-(5-methylfuran-2-yl)-ethoxycarbonyl (Epoc) group. The Epoc group was transformed into an Fmoc-like structure with gold(iii)-catalyzed fluorene formation and was removable under Fmoc-like mild basic conditions post-transformation even though it was originally stable under strongly basic conditions. As an application for organic synthesis, the Epoc group provides the novel orthogonality of gold(iii)-labile protecting groups in solid-phase peptide synthesis. In addition, the high turnover number of fluorene formation in aqueous media is suggestive of the applicability of the Epoc group to biological systems.A protecting group removable with gold(iii)-catalyzed fluorene formation and the subsequent addition of piperidine was developed. 相似文献
36.
Ohno H Wakayama R Maeda S Iwasaki H Okumura M Iwata C Mikamiyama H Tanaka T 《The Journal of organic chemistry》2003,68(15):5909-5916
Alkyl radicals generated by treatment of thiocarbamates of conformationally favorable 3-alkyl-3-arylpropan-1-ols with tris(trimethylsilyl)silane and AIBN efficiently undergo intramolecular ipso substitution of the methoxy group, yielding the corresponding cyclized products. In contrast, either conformationally favorable or flexible 1-arylalkan-3- or 4-ones easily cyclize into five- or six-membered condensed rings by treatment with SmI(2) via ketyl radical intermediates. The addition of HMPA as cosolvent dramatically changes the cyclization mode of the SmI(2)-induced reaction, and the para-cyclization products are exclusively formed. This "HMPA effect" can be rationalized by the strong chelating ability of HMPA with the samarium atom. 相似文献
37.
Katsunori Teranishi 《Journal of inclusion phenomena and macrocyclic chemistry》2002,44(1-4):313-316
A useful technique to bifunctionalize the secondary hydroxyl faces of cyclodextrins is described. Regioselective2A,2D-disulfonylations ofcyclodextrins were achieved by reacting cyclodextrins with a combinationof a novel disulfonyl imidazole reagent and molecular sieves inN,N-dimethylformamide. The resulting disulfonates were convertedto 2A,3A,2D,3D-dimannoepoxy-cyclodextrins and3A,3D-diamino-3A,3D-dideoxy-(2AS,3AS),(2DS,3DS)-cyclodextrins, which contain twofunctional groups on the periphery of the molecules. 相似文献
38.
[reaction: see text]. The zirconium-mediated intramolecular ester transfer reaction of N-alkenyl carbamate derivatives proceeded to give alpha-substituted gamma-aminobutyric acid (GABA) derivatives in good to excellent yields. Quenching experiments of the reaction mixture with iodine or O2 indicated the presence of a cyclopropane intermediate. The resulting iodide was converted to 2-substituted pyrrolidine-3-carboxylate and/or alpha-alkylidene-gamma-aminobutyric acid derivatives in a stereospecific manner. 相似文献
39.
Dithienylethenes with a novel photochromic performance 总被引:2,自引:0,他引:2
Dithienylethenes with low decoloration quantum yields and thermal reversibility at high temperature above 100 degrees C were prepared. Introduction of bulky alkoxy substituents at 2- and 2'-positions of the thiophene rings strongly suppressed the cycloreversion quantum yields. The quantum yields were lower than 10(-3), and the photogenerated color remained stable enough under room light. On the other hand, the bulky alkoxy substituent decreased the thermal stability of the colored closed-ring isomers at high temperature. The color of the dithienylethene with cyclohexyloxy substituents faded out in less than 1 min at 160 degrees C. 相似文献
40.
Mitsuhiro Iwasaki Yukatsu Shichibu Katsuaki Konishi 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(8):2465-2469
It is well known that alkynes act as π‐acids in the formation of complexes with metals. We found unprecedented attractive Au–π interactions in diacetylene‐modified [core+exo]‐type [Au8]4+ clusters. The 4‐phenyl‐1,3‐butadiynyl‐modified cluster has unusually short Au–Cα distances in the crystal structure, revealing the presence of attractive interactions between the coordinating C≡C moieties and the neighboring bitetrahedral Au6 core, which is further supported by IR and NMR spectra. Such weak interactions are not found in mono‐acetylene‐modified clusters, which indicates that they are specific for diacetylenic ligands. The attractive Au–π interactions are likely associated with the low energy of the π* orbital in the diacetylenic moieties, into which the valence electrons of the gold core may be back donated. The [Au8]4+ clusters show clear red‐shifts of >10 nm with respect to the corresponding mono‐acetylenic clusters in UV/Vis absorption bands, which indicates substantial electronic perturbation effects of the Au–π interactions. 相似文献