- Manganese-Catalyzed Hydroarylation of Unactivated Alkenes
-
Transition-metal-catalyzed hydroarylation of unactivated alkenes with strategic use of remote coordinating functional groups has received significant attention recently to address the issues of both low reactivity and poor selectivity. The bidentate 8-aminoquinoline amide group is the most successfully adopted in unactivated alkenes for Pd and Ni catalysis. We describe the first manganese-catalyzed hydroarylation of unactivated alkenes bearing diverse simple functionalities with arylboronic acids. A series of δ- and γ-arylated amides, ketones, pyridines, and amines was accessed with excellent regioselectivity and in high yields. Hydroalkenylation of unactivated alkenes was also shown to be applicable under this manganese-catalysis regime. The method features earth-abundant manganese catalysis, easily available substrates, broad functional-group tolerance, and excellent regioselective control.
- Liu, Ting,Wang, Congyang,Yang, Yunhui
-
supporting information
p. 14256 - 14260
(2020/07/13)
-
- Effects of lipophilicity, protecting group and stereochemistry on the antimalarial activity of carbohydrate-derived thiochromans
-
A series of novel carbohydrate-derived thiochromans has been successfully synthesized in order to investigate the influence of alkyl substituents on the aromatic ring of the thiophenol moiety in addition to the effect of protecting groups and stereochemistry on the sugar component of the target molecules. Results from the evaluation of the thiochromans for their antimalarial activity against the chloroquine-sensitive (3D7) strain of Plasmodium falciparum suggest that the presence of short chain alkyl substituents, a benzyl ether protecting group and equatorial orientation of the C-4 substituent on the sugar moiety are crucial structural features that impart high antimalarial activity.
- Madumo, Gilbert K.,Moshapo, Paseka T.,Kinfe, Henok H.
-
p. 817 - 833
(2018/01/10)
-
- Chiral isoxazolidine-mediated stereoselective umpolung α-phenylation of methyl ketones
-
An effective asymmetric α-phenylation of methyl ketones with triphenylaluminium in the presence of (+)-benzopyranoisoxazolidine has been developed. The reaction proceeds via the in situ formation of a chiral N-alkoxyenamine and the subsequent diastereoselective nucleophilic phenylation to provide α-phenylated products in moderate to good yields, with high enantioselectivities.
- Takeda, Norihiko,Furuishi, Mizuki,Nishijima, Yuri,Futaki, Erika,Ueda, Masafumi,Shinada, Tetsuro,Miyata, Okiko
-
supporting information
p. 8940 - 8943
(2018/12/10)
-
- Organic photocatalysis for the radical couplings of boronic acid derivatives in batch and flow
-
We report an acridium-based organic photocatalyst as an efficient replacement for iridium-based photocatalysts to oxidise boronic acid derivatives by a single electron process. Furthermore, we applied the developed catalytic system to the synthesis of four active pharmaceutical ingredients (APIs). A straightforward scale up approach using continuous flow photoreactors is also reported affording gram an hour throughput.
- Lima, Fabio,Grunenberg, Lars,Rahman, Husaini B. A.,Labes, Ricardo,Sedelmeier, Joerg,Ley, Steven V.
-
supporting information
p. 5606 - 5609
(2018/06/04)
-
- Hydrogen-transfer reduction of α,β-unsaturated carbonyl compounds catalyzed by naphthyridine-functionalized N-heterocyclic carbene complexes
-
Substitution of silver complex of 2-chloro-7-(mesitylimidazolylidenylmethyl)naphthyridine (NpNHC) with palladium(II), rhodium(I) and iridium(I) metal precursors provided [Pd(C,N-NpNHC)(η3-allyl)](BF4) (5), RhCl(COD)(C-NpNHC) (6a) and IrCl(COD)(C-NpNHC) (6b), respectively. Abstraction of chloride from 6a and 6b with AgBF4 provided the chelation complexes [Rh(COD)(C,N-NpNHC)](BF4) (7a) and Ir(COD)(C,N-NpNHC)(BF4) (7b), respectively. All complexes were characterized using NMR and elemental analyses and the structural details of 5 and 6a were further confirmed using X-ray crystallography. In catalytic activity studies, complex 5 was found to be an effective catalyst in the hydrogen-transfer reduction of α,β-unsaturated carbonyl compounds into the corresponding saturated carbonyl compounds.
- Huang, Hsiao-Ching,Ramanathan, Mani,Liu, Yi-Hong,Peng, Shie-Ming,Liu, Shiuh-Tzung
-
-
- 2-AMINO-1,3,4-THIADIAZINE AND 2-AMINO-1,3,4-OXADIAZINE BASED ANTIFUNGAL AGENTS
-
The invention provides a compound which is a diazine of formula (I) or a tautomer thereof, or a pharmaceutically acceptable salt thereof, for use as an antifungal agent: (I) wherein X, N', C', A and E are as defined herein. The invention also provides a compound of Formula (I) as defined herein.
- -
-
Page/Page column 51
(2017/02/09)
-
- A Lewis Base Catalysis Approach for the Photoredox Activation of Boronic Acids and Esters
-
We report herein the use of a dual catalytic system comprising a Lewis base catalyst such as quinuclidin-3-ol or 4-dimethylaminopyridine and a photoredox catalyst to generate carbon radicals from either boronic acids or esters. This system enabled a wide range of alkyl boronic esters and aryl or alkyl boronic acids to react with electron-deficient olefins via radical addition to efficiently form C?C coupled products in a redox-neutral fashion. The Lewis base catalyst was shown to form a redox-active complex with either the boronic esters or the trimeric form of the boronic acids (boroxines) in solution.
- Lima, Fabio,Sharma, Upendra K.,Grunenberg, Lars,Saha, Debasmita,Johannsen, Sandra,Sedelmeier, Joerg,Van der Eycken, Erik V.,Ley, Steven V.
-
supporting information
p. 15136 - 15140
(2017/11/20)
-
- A simple route to 1,4-addition reactions by Co-catalyzed reductive coupling of organic tosylates and triflates with activated alkenes
-
An efficient Co-catalyzed 1,4-addition reaction of alkyl/aryl triflates and tosylates with activated alkenes is described. In this reaction, an air-stable cobalt(ii) complex, a mild reducing agent Zn and a simple proton source (H2O) are used. A radical mechanism for the addition of alkyl tosylates to activated alkenes is likely involved.
- Hsieh, Jen-Chieh,Chu, Yi-Hua,Muralirajan, Krishnamoorthy,Cheng, Chien-Hong
-
p. 11584 - 11587
(2017/10/27)
-
- Hydrodecarboxylation of Carboxylic and Malonic Acid Derivatives via Organic Photoredox Catalysis: Substrate Scope and Mechanistic Insight
-
A direct, catalytic hydrodecarboxylation of primary, secondary, and tertiary carboxylic acids is reported. The catalytic system consists of a Fukuzumi acridinium photooxidant with phenyldisulfide acting as a redox-active cocatalyst. Substoichiometric quantities of Hünigs base are used to reveal the carboxylate. Use of trifluoroethanol as a solvent allowed for significant improvements in substrate compatibilities, as the method reported is not limited to carboxylic acids bearing α heteroatoms or phenyl substitution. This method has been applied to the direct double decarboxylation of malonic acid derivatives, which allows for the convenient use of dimethyl malonate as a methylene synthon. Kinetic analysis of the reaction is presented showing a lack of a kinetic isotope effect when generating deuterothiophenol in situ as a hydrogen atom donor. Further kinetic analysis demonstrated first-order kinetics with respect to the carboxylate, while the reaction is zero-order in acridinium catalyst, consistent with another finding suggesting the reaction is light limiting and carboxylate oxidation is likely turnover limiting. Stern-Volmer analysis was carried out in order to determine the efficiency for the carboxylates to quench the acridinium excited state.
- Griffin, Jeremy D.,Zeller, Mary A.,Nicewicz, David A.
-
supporting information
p. 11340 - 11348
(2015/09/21)
-
- Palladium on charcoal as a catalyst for stoichiometric chemo- and stereoselective hydrosilylations and hydrogenations with triethylsilane
-
Stoichiometric quantities of triethylsilane in the presence of activated Pd/C as the catalyst can be used to effect chemo-, regio-, and stereoselective hydrosilylation and transfer hydrogenation reactions. α,β-Unsaturated aldehydes and ketones are selectively hydrosilylated to give the corresponding enol silanes or transfer hydrogenated to give the saturated carbonyl compounds in the presence of other reducible functional groups.
- Tuokko, Sakari,Pihko, Petri M.
-
p. 1740 - 1751
(2015/02/19)
-
- Synthesis and neuroprotective effect of E-3,4-dihydroxy styryl aralkyl ketones derivatives against oxidative stress and inflammation
-
E-3,4-Dihydroxy styryl aralkyl ketones as well as their 3,4-diacetylated derivatives as the analogues of neuroprotective agent CAPE were designed and synthesized for improving stability and lipid solubility. The neuroprotective activities of target compounds 10a-g and 11a-g were tested by three models in vitro, including 1,1-diphenyl-2-picrylhydrazyl radical scavenging capacity, neuronal protecting effect against damage induced by H2O2 in PC12 cells and nitric oxide suppression effect in BV2 microglial cells. The results demonstrated that compounds 10f and 11f exhibited the most potent neuroprotective effect against oxidative stress and inflammation, which is higher than that of the lead compound CAPE.
- Ning, Xianling,Guo, Ying,Ma, Xiaoyan,Zhu, Renzong,Tian, Chao,Wang, Xiaowei,Ma, Zhizhong,Zhang, Zhili,Liu, Junyi
-
p. 3700 - 3703
(2013/07/25)
-
- Improving the atom efficiency of the wittig reaction by a "waste as catalyst/Co-catalyst" strategy
-
(Figure Presented) Waste not want not: Reported is a strategy to improve the atom economy of the Wittig reaction by using it in tandem reactions that directly employ the wastePh3PO as an in-situ-generated Lewis base catalyst/co-catalyst in the next step (see scheme).
- Cao, Jun-Jie,Zhou, Feng,Zhou, Jian
-
supporting information; experimental part
p. 4976 - 4980
(2010/09/08)
-
- Organic electrosynthesis using toluates as simple and versatile radical precursors
-
The electrolysis of toluate esters leads smoothly to the formation of the radical of the alkyl fragment. This property has been used to develop a new electrochemical deoxygenation reaction. The Royal Society of Chemistry.
- Lam, Kevin,Marko, Istvan E.
-
experimental part
p. 95 - 97
(2009/03/11)
-
- Cobalt-catalyzed reductive coupling of saturated alkyl halides with activated alkenes
-
An efficient cobalt-catalyzed reductive coupling reaction of alkyl halides with electron-withdrawing alkenes (CH2=CR1EWG, EWG = electron-withdrawing group) in the presence of water and zinc powder in acetonitrile to give the corresponding Michael-type addition product (RCH 2CR1EWG) was described. The methodology is versatile such that unactivated primary, secondary, and tertiary alkyl bromides and iodides and various conjugated alkenes including acrylates, acrylonitrile, methyl vinyl ketone, and vinyl sulfone all successfully participate in this coupling reaction. For the alkyl halides used in the reaction, the iodides generally gave heller yields compared to those of the corresponding bromides. It is a unique method employing CoI2dppe, zinc, and alkyl halides, affording conjugate addition products in high yields. Mechanistically, the reaction appears to follow an oxidative addition driven route rather than the previously reported radical route.
- Shukla, Paritosh,Hsu, Yun-Chu,Cheng, Chien-Hong
-
p. 655 - 658
(2007/10/03)
-
- Synthesis and DHFR inhibitory activity of a series of 6-substituted-2,4-diaminothieno[2,3-d]pyrimidines
-
A series of 6-aralkyl substituted 2,4-diaminothieno[2,3-d]pyrimidines in which the 6-aryl group is separated from the thieno[2,3-d]pyrimidine ring by two to five methylene groups were synthesized and studied as inhibitors of dihydrofolate reductase from Pneumocystis carinii, Toxoplasma gondii, Mycobacterium avium, and rat liver. Compounds in which the thieno[2,3-d]pyrimidine ring is separated from the 6-aryl substituent by three methylene groups were the most potent inhibitors of the series (with IC50 values ranging from 0.24 and 11.0 μM) but those with two methylene groups between the aromatic rings were the most selective agents.
- Donkor, Isaac O.,Li, Hui,Queener, Sherry F.
-
p. 605 - 611
(2007/10/03)
-
- Intramolecular reactions of benzylic azides with ketones: Competition between Schmidt and Mannich pathways
-
The Lewis acid-promoted reactions of benzylic azides with ketones can proceed by two major pathways. The azido-Schmidt reaction involves simple addition of azide to the ketone followed by rearrangement and ring expansion. In addition, benzylic azides can undergo prior rearrangement to afford iminium ions that can subsequently participate in a Mannich reaction. A series of ketones containing an α CH2(CH2)nCH(N3)Ph substituent (n = 1-3) was prepared to investigate the dependence of products on ketone ring size and tether length. For all ketones examined, good yields of bicyclic lactams arising from intramolecular Schmidt reaction were obtained when a four-carbon linker was used (n = 1 in the above formulation), but Mannich products predominated for the longer tethers examined (n = 2, 3).
- Wrobleski,Aube
-
p. 886 - 889
(2007/10/03)
-
- Aryl 1-chloroalkyl sulfoxides as acyl anion equivalents: A new synthesis of vinyl sulfides, ketones, and diketones from aryl 1-chloroalkyl sulfoxides and α,ω-dichloro-α,ω-disulfinylalkanes
-
Treatment of aryl α-chloroalkyl sulfoxides, which were synthesized from aryl 1-chloroalkyl sulfoxides by alkylation with iodoalkanes, with trifluoroacetic anhydride and NaI in acetone at low temperature afforded vinyl sulfides in high yields. The vinyl sulfides were converted to ketones by hydrolysis with HClO4 in refluxing 1,4-dioxane in good yields. In this procedure, the lithiated aryl 1-chloroalkyl sulfoxides acted as acyl anion equivalents. The procedure was extended to a synthesis of α,ω-diketones starting from α,ω-dichloro-α,ω-disulfinylalkanes. The procedure was found to work well when the length of the carbon chain of the α,ω-disulfinylalkanes is longer than four, and the yields of the diketones were found to be somewhat variable (60-80%).
- Satoh, Tsuyoshi,Taguchi, Daisaku,Suzuki, Chihiro,Fujisawa, Satoshi
-
p. 493 - 500
(2007/10/03)
-
- Reactions of acylzirconocene chloride with nucleophiles: Bimodal reactivity at β- and acyl carbons of α,β-unsaturated acylzirconocene chloride
-
Reactions of α,β-unsaturated acylzirconocene chloride with nucleophiles showed novel bimodal reactivity at the β- and acyl carbons depending upon the nucleophile employed, and the formation of ketone α,β-dianionic species was also observed. (C) 2000 Elsev
- Hanzawa,Narita,Kaku-uchi,Taguchi
-
p. 7525 - 7528
(2007/10/03)
-
- Diazo decomposition in the presence of tributyltin hydride. Reduction of α-diazo carbonyl compounds
-
The diazo group of a series of α-diazo carbonyl compounds can be reduced to the corresponding CH2 group by Bu3SnH under Cu(acac)2-catalytic or photochemical conditions. The mechanistic aspects of this reaction were investigated in some detail, and a possible reaction pathway was discussed. (C) 2000 Elsevier Science Ltd.
- Tan, Zhongping,Qu, Zhaohui,Chen, Bei,Wang, Jianbo
-
p. 7457 - 7461
(2007/10/03)
-
- Solvolysis of 2,2-dialkylvinyl iodonium salt: Alkyl participation and possibility of a primary vinylic cation intermediate
-
Solvolysis of (E)- and (Z)-2-methyl-5-phenyl-1-pentenyl(phenyl)iodonium tetrafiuoroborate (1·BF4) was carried out in various alcohols, acetic acid, and aqueous solutions at 60 °C. Products (after acid hydrolysis) include iodobenzene and 2-methyl-5-phenylpentanal as well as rearranged ones: 6- phenyl-2-hexanone, 6-phenyl-3-hexanone, 6-phenyl-2-hexyne, 6-phenyl- 1,2- hexadiene, and 6-phenyl-2,3-hexadiene. The products of α-elimination, including 1-methyl-3-phenyl-1-cyclopentene, were also obtained in methanol and ethanol. Solvolysis of the E isomer (E)-1 is faster than that of (Z)-1 in every solvent examined. The percentage of rearrangement is higher with (E)-1 than with (Z)-1, and the main rearranged products are those of migration of the alkyl group trans to the iodonio group, but migration of the cis alkyl group is also involved. Theoretical calculations suggest that interconversion between the secondary Vinylic cations by 1,2-hydride shift is rapid. These results show that a major heterolysis reaction occurs with β-alkyl participation to directly give a secondary vinylic cation, but stereochemistry of the unrearranged substitution products suggests that formation of the primary vinylic cation is also involved in less nucleophilic solvents like acetic acid and 2,2,2-trifluoroethanol.
- Okuyama, Tadashi,Yamataka, Hiroshi,Ochiai, Masahito
-
p. 2761 - 2769
(2007/10/03)
-
- Solvolysis of β,β-dialkylvinyliodonium salt: Primary vinyl cation intermediate and alkyl participation
-
Solvolysis of both E and Z isomers of a β,β-dialkylvinyl-(phenyl)iodonium salt gave extensively rearranged products. A mechanism involving a primary vinyl cation intermediate as well as the alkyl participation leading to secondary vinyl cations is proposed.
- Okuyama, Tadashi,Sato, Koichi,Ochiai, Masahito
-
p. 1177 - 1178
(2007/10/03)
-
- Highly controlled chemoselectivity of tin enolate by its hybridization state. Anionic complex of tin enolate coordinated by tetrabutylammonium bromide as halo selective reagent
-
The control of reactivity and/or selectivity of organotin(IV) enolates has been studied by means of a high coordination method in which the hybridization state of tin was effectively changed. An anionic tin complex, five-coordinated tin enolate 1(h), was formed by the coordination of bromide anion from tetrabutylammonium bromide (Bu4NBr) to neutral four-coordinated tin(IV) enolates 1(e). The highly coordinated enolates which attained a marked change in chemoselectivity have higher nucleophilicity to organic halides. In addition, they showed low nucleophilicity toward carbonyl moieties by the coordination of the bromide anion, whereas carbonyl addition readily proceeds using the usual four-coordinated tin enolate. NMR studies revealed the generation of HMPA- or bromide-anion-coordinated tin enolates in equilibrium between four-coordinated enolate 1c(e) and five-coordinated enolate 1c(h), showing a considerable upfield shift δ(119Sn) and increasing values of the coupling constants 1J(119Sn-13C). In detailed NMR analyses of highly coordinated tin enolate, it was shown that the contribution of highly coordinated species 1(h) to the equilibrium between 1(e) and 1(h) became more significant as the added amount of ligands such as Bu4NBr or HMPA was increased. Considering these results, it was assumed that the bromide-anion-coordinated tin enolate was generated, which showed a unique reactivity and selectivity. The effective control of chemoselectivity in the intermolecularly competitive reaction between organic halides and carbonyl compounds was demonstrated using two types of tin enolates, four-coordinated enolate and highly coordinated anionic enolate; halide displacement reaction exclusively took place using the bromide-anion-coordinated enolate, and the usual four-coordinated enolates reacted with only carbonyl compounds.
- Yasuda, Makoto,Hayashi, Keiko,Katoh, Yasuhiro,Shibata, Ikuya,Baba, Akio
-
p. 715 - 721
(2007/10/03)
-
- Copper-Catalyzed Conjugate Additions of Organozirconocenes. Synthetic and Mechanistic Studies.
-
In the presence of 3-10 mol percent of Cu(I) salts such as CuBr*SMe2 or CuCN, alkylzirconocenes add readily to α,β-unsatuatred ketones, aldehydes, and sulfones.The reaction yield is sensitive to the presence of Lewis acids and bases.Steric hindrance as well as a broad range of functional groups are tolerated in the conjugate addition process.Unsaturated N-acyl oxazolidinones give high diastereoselectivities for the formation of the new asymmetric carbon.The resulting zirconium enolates can be used for tandem aldol addition reactions to aldehydes.Depending on the type of copper salt used, slow or fast formation of copper mirror occurs, but no intermediate copper species is detected spectroscopically.Therefore, a mechanism involving enone complexation by the Lewis-acidic zirconocene followed by inner-spere transfer of the alkyl substituent to chelated Cu(I) is proposed.
- Wipf, Peter,Xu, Wenjing,Smitrovich, Jacqueline H.,Lehmann, Roman,Venanzi, Luigi M.
-
p. 1935 - 1954
(2007/10/02)
-
- Transmetalation Reactions of Alkylzirconocenes: Copper-Catalyzed Conjugate Addition to Enones
-
Rapid hydrozirconation of alkenes by zirconocene hydrochloride, followed by addition of 1 equiv of enone and catalytic amounts of Cu(I) salts, led to the corresponding 1,4-addition products in moderate to high yields and provided the first protocol for in situ preparation of alkyl cuprates from alkenes.
- Wipf, Peter,Smitrovich, Jacqueline H.
-
p. 6494 - 6496
(2007/10/02)
-
- Direct Formation and Subsequent Substitution of Remote Ketone-Functionalized Organocopper Reagents
-
Remote ketone-functionalized aryl- and alkylcopper reagents have been synthesized by the use of a highly activated form of zero-valent copper. 5-Bromo-2-pentanone and 4-iodobenzophenone undergo oxidative addition with activated copper to form 5-cuprio-2-pentanone and 4-cupriobenzophenone, respectively.These, in turn, can be cross-coupled with alkyl halides to produce the corresponding alkylated ketones and with acid chlorides to form the corresponding diketones.By use of this methodology, a two-step, one-pot synthesis of methyl (E)-9-oxo-2-decenoate and 8-nonen-2-one have been achieved.The former compound is the methyl ester of the "queen substance" of the honey bee, and the latter is part of an "attractant mixture" for cheese mites found in cheddar cheese.These syntheses were accomplished by converting commercially available 6-bromo-2-hexanone to 6-cuprio-2-hexanone followed by cross-coupling with commercially available methyl 4-bromocrotonate and allyl bromide, respectively.
- Ebert, Greg W.,Klein, Walter R.
-
p. 4744 - 4747
(2007/10/02)
-
- Synthesis of aryl-substituted aldehydes and ketones via palladium-catalyzed coupling of aryl halides and non-allylic unsaturated alcohols
-
The palladium-catalyzed coupling of aryl halides and non-allylic unsaturated alcohols affords excellent yields of aryl-substituted aldehydes and ketones.
- Larock,Leung,Stolz-Dunn
-
p. 6629 - 6632
(2007/10/02)
-
- Highly Chemoselective Palladium-Catalyzed Conjugate Reduction of α,β-Unsaturated Carbonyl Compounds with Silicon Hydrides and Zinc Chloride Cocatalyst
-
A three-component system comparised of a soluble palladium catalyst, hydridosilane, and zinc chloride is capable of efficient conjugate reduction of α,β-unsaturated ketones and aldehydes.The optimal set of condition includes diphenylsilane as the most effective hydride donor, any soluble palladium complex in either the 0 or II oxidation state, when it is stabilized by phosphine ligands, and ZnCl2 as the best Lewis acid cocatalyst.The reaction is very general with respect to a broad range of unsaturated ketones and aldehydes, and it is highly selective for these Michael acceptors, as reduction of α,β-unsaturated carboxylic acid derivatives is very sluggish under these conditions.When dideuteriodiphenylsilane is used to reduce unsaturated ketones, deuterium is stereoselectively introduced at the less-hindered face of the substrate and regioselectively at the β-position.Conversely, when reductions are carried out in the presence of traces of D2O, deuterium incorporation occurs at the α-position.On the basis of deuterium-incorporation experiments and 1H NMR studies, a catalytic cycle is postulated in which the first step involves reversible coordination of the palladium complex to the electron-deficient olefin and oxidative addition of silicon hydride to form a hydropalladium olefin complex.Migratory insertion of hydride into the coordinated olefin produces an intermediate palladium enolate which, via reductive elimination, collapses back to the Pd(0) complex and a silyl enol ether, which is then hydrolyzed to the saturated ketone.In addition to catalyzing that hydrolysis, ZnCl2 facilitates the hydrosilation process.
- Keinan, Ehud,Greenspoon, Noam
-
p. 7314 - 7325
(2007/10/02)
-
- Synthesis of diarylheptanoids and assessment of their pungency
-
With the aim of correlating pungency with substituent groups on one benzene ring, various analogues of yakuchinones were synthesized by means of the Claisen-Schmidt reaction. Their pungencies were assessed by direct comparison of the threshold concentrations obtained in taste experiments. The presence of a phenolic hydroxyl group was indispensable for high pungency, while that of a 1,2-double bond of the heptanone part tended to decrease the pungency.
- Itokawa,Aiyama,Ikuta
-
p. 2491 - 2496
(2007/10/02)
-