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71.
Abura T Ogo S Watanabe Y Fukuzumi S 《Journal of the American Chemical Society》2003,125(14):4149-4154
This paper reports the isolation and structural determination of a water-soluble hydride complex [Cp*Ir(III)(bpy)H](+) (1, Cp* = eta(5)-C(5)Me(5), bpy = 2,2'-bipyridine) that serves as a robust and highly active catalyst for acid-catalyzed transfer hydrogenations of carbonyl compounds at pH 2.0-3.0 at 70 degrees C. The catalyst 1 was synthesized from the reaction of a precatalyst [Cp*Ir(III)(bpy)(OH(2))](2+) (2) with hydrogen donors HCOOX (X = H or Na) in H(2)O under controlled conditions (2.0 < pH < 6.0, 25 degrees C) which avoid protonation of the hydrido ligand of 1 below pH ca. 1.0 and deprotonation of the aqua ligand of 2 above pH ca. 6.0 (pK(a) value of 2 = 6.6). X-ray analysis shows that complex 1 adopts a distorted octahedral geometry with the Ir atom coordinated by one eta(5)-Cp*, one bidentate bpy, and one terminal hydrido ligand that occupies a bond position. The isolation of 1 allowed us to investigate the robust ability of 1 in acidic media and reducing ability of 1 in the reaction with carbonyl compounds under both stoichiometric and catalytic conditions. The rate of the acid-catalyzed transfer hydrogenation is drastically dependent on pH of the solution, reaction temperature, and concentration of HCOOH. The effect of pH on the rate of the transfer hydrogenation is rationalized by the pH-dependent formation of 1 and activation process of the carbonyl compounds by protons. High turnover frequencies of the acid-catalyzed transfer hydrogenations at pH 2.0-3.0 are ascribed not only to nucleophilicity of 1 toward the carbonyl groups activated by protons but also to a protonic character of the hydrido ligand of 1 that inhibits the protonation of the hydrido ligand. 相似文献
72.
Vilsmeier–Haack‐type cyclization of 1H‐indole‐4‐propanoic acid derivatives was examined as model construction for the A–B–C ring system of lysergic acid ( 1 ). Smooth cyclization from the 4 position of 1H‐indole to the 3 position was achieved by Vilsmeier–Haack reaction in the presence of K2CO3 in MeCN, and the best substrate was found to be the N,N‐dimethylcarboxamide 9 (Table 1). The modified method can be successfully applied to an α‐amino acid derivative protected with an N‐acetyl function, i.e., to 27 (Table 2); however, loss of optical purity was observed in the cyclization when a chiral substrate (S)‐ 27 was used (Scheme 5). On the other hand, the intramolecular Pummerer reaction of the corresponding sulfoxide 20 afforded an S‐containing tricyclic system 22 , which was formed by a cyclization to the 5 position (Scheme 3). 相似文献
73.
A simple method has been described for the Spectrophotometric determination of cobalt(II) with 2-(3′-sulfobenzoyl)pyridine benzoylhydrazone (SBPBH). In aqueous solution, cobalt(II) reacts with SBPBH to form a yellow complex, which is not destroyed even by the addition of 3.8 M perchloric acid. The absorption maximum of the complex in 1.5 M perchloric acid medium was found to be 400 nm; the molar absorptivity was 2.17 × 104 liters mol−1 cm−1. The proposed method is fairly selective and has been applied to the determination of cobalt in standard alloy steel samples. 相似文献
74.
Kobayashi S Nakamura Y Maehara T Hamashima H Sasatsu M Asano K Ohishi Y Tanaka A 《Chemical & pharmaceutical bulletin》2001,49(9):1053-1060
We show that the topological significance of the gel mobility of cis-diamminedichloroplatinum(II) (DDP)-closed circular DNA (ccDNA) adducts decreases with reaction time, until a point at which it joins relaxed DNA, and that the mobility of the adducts increases again. There is no relationship between the relative length of the adducts and the gel mobility. Although the significance of the decrease of gel mobility is due to the unwinding of cis-DDP-DNA (or trans-DDP-DNA) adducts, the conformational significance of the subsequent increase in mobility is unclear. To elucidate the conformational significance for unwinding of the adducts, we measured the writhing number (Wk) of the adducts using electron microscopy and analyzed the topological states of cis-DDP (or trans-DDP) adducts based on the White rule, Lk=Wk+Tk. Where, Lk and Tk represent the linking and twisting number in the ring, respectively. From the data, we found that the Wk of cis-DDP-ccDNA adducts in comparison with trans-DDP-ccDNA adducts increases from a negative to a positive number with time. This suggests that cis-DDP plays a role in the change of the topological state of ccDNA. In the abstraction of platinum from the adducts with CN- ion, the differences in both topological states may explain why Pt in trans-DDP is abstracted more easily than in cis-DDP. To explain the abstraction of Pt ion, we also discuss the findings based on the thermodynamic cycle in a intermolecular crosslink model Pt(NH3)2(guanine)2(2+)-->Pt(CN)4(2-) using the Pt parametrized PM3 method. 相似文献
75.
Shoji Asano Keiji Itano Kohfuku Kohda Yuriko Yamagata 《Journal of heterocyclic chemistry》1996,33(4):1115-1121
Reaction of 9-substituted (methyl or benzyl) 1-aminoadenines 1 with hydrazine afforded 9-substituted 6-hydrazinopurines 2 and 1-substituted 5-ammo-4-(4-amino-1,2,4-triazol-3-yl)imidazole ( 4 ). The product ratio of 2 to 4 rose with increasing amounts of methanol used as the solvent. When the same reaction was carried out using 1,9-dimethyladenine instead of 1 , compounds 2 and 4 were also obtained with N6,9-dimethyladenine. A possible mechanism for formation of 2 and 4 is discussed. 相似文献
76.
Wang CR Kai T Tomiyama T Yoshida T Kobayashi Y Nishibori E Takata M Sakata M Shinohara H 《Angewandte Chemie (International ed. in English)》2001,40(2):265
The cover picture shows a section of the electron charge density of the first metal carbide endohedral metallofullerene (Sc(2)C(2))@C(84) obtained from a synchrotron X-ray powder diffraction study by the maximum entropy method (MEM). The several density maxima, which correspond to scandium and carbon atoms, are clearly seen inside the C(84) carbon cage. The MEM charge density distribution also reveals that the C(84) cage has D(2d) symmetry (no. 23) and that the C(2) axis is parallel to the <100> face-centered cubic (fcc) direction of the unit cell. As a consequence of the site symmetry being 4mm, the C(2) axis of (Sc(2)C(2))@C(84) is oriented to six equivalent <100> directions and shows a merohedral disorder. The resultant Sc small middle dot small middle dot small middle dotSc distances and C-C bond lengths of the Sc(2)C(2) cluster are 0.429(2) and 0.142(6) nm, respectively. The observed C-C bond length is between that of a typical single and a double bond, and is very close to that of the C-C bond (0.143 nm) combining two pentagons in a C(60) molecule. More about this fascinating structure can be found in the contribution by Shinohara and co-workers on p. 397 ff. 相似文献
77.
Torizawa T Ono AM Terauchi T Kainosho M 《Journal of the American Chemical Society》2005,127(36):12620-12626
The unambiguous assignment of the aromatic ring resonances in proteins has been severely hampered by the inherently poor sensitivities of the currently available methodologies developed for uniformly 13C/15N-labeled proteins. Especially, the small chemical shift differences between aromatic ring carbons and protons for phenylalanine residues in proteins have prevented the selective observation and unambiguous assignment of each signal. We have solved all of the difficulties due to the tightly coupled spin systems by preparing regio-/stereoselectively 13C/2H/15N-labeled phenylalanine (Phe) and tyrosine (Tyr) to avoid the presence of directly connected 13C-1H pairs in the aromatic rings. The superiority of the new labeling schemes for the assignment of aromatic ring signals is clearly demonstrated for a 17 kDa calcium binding protein, calmodulin. 相似文献
78.
[reaction: see text] In the presence of MS 4A in DMSO, cyanobenzoylation of various aldehydes with benzoyl cyanide proceeded very smoothly to give the corresponding cyanohydrin benzoates in high to excellent yields without an acid or a base. On the other hand, reaction of aldehydes with BzCN in DMSO-H(2)O also occurred readily to afford the corresponding free cyanohydrins exclusively. 相似文献
79.
(Ss)-3-(p-Tolylsufinyl)-2-furaldimine was synthesized, and condensation of the chiral furaldimine with lithium ester enolates has been examined. The product distribution of the reaction is dependent upon reaction conditions and on the kind of the substituent placed on the esters. Disubstituted ester enolate resulted in the exclusive formation of (4R)-beta-lactam, while unsubstituted, tert-butyl ester enolate preferentially gave (3R)-beta-amino ester. With the monosubstituted ester enolates, the condensation afforded (4R)-beta-lactams and/or (3R)-beta-amino esters as major products. This method has been applied to an efficient route to chiral furyl beta-lactams. 相似文献
80.
J. Koarashi K. Akiyama T. Asano T. Yokota 《Journal of Radioanalytical and Nuclear Chemistry》2005,262(3):771-774
The effects of incorporating tritiated water into a 14C-sampling system in sample preparation and 14C activity measurement by liquid scintillation counting were investigated. Experiments derived the limit of water content in the prepared sample, and also demonstrated that 14C activity can be determined without any interference from 3H contamination for a clear-sample solution. The results enabled us to estimate the permissible relative humidity of air required for accomplishing sample preparation and 14C activity measurement. These showed that for sampling of air with less than the permissible relative humidity, total 14C activity in airborne effluent can be evaluated accurately without dehumidification of air.The authors would like to thank T. Kozawa, K. Isaka and Y. Adachi of Inspection Development Company Ltd., Y. Hiyama of Zuihou Sangyou Company Ltd., and T. Mizutani, H. Watanabe, M. Takeishi and K. Shinohara of Japan Nuclear Cycle Development Institute for their valuable assistance. 相似文献