著者
新森 英之 大須賀 篤弘
出版者
The Society of Synthetic Organic Chemistry, Japan
雑誌
有機合成化学協会誌 (ISSN:00379980)
巻号頁・発行日
vol.57, no.9, pp.749-762, 1999-09-01 (Released:2009-11-16)
参考文献数
64
被引用文献数
7 9

Recent advances in the synthesis of covalently linked multiporphyrin arrays are summarized with particular emphasis on those with well-defined geometries and with novel and interesting properties. Of these, 1) aromatic-group bridged porphyrin arrays have been proved to be useful for defining geometries of the porphyrin arrays without alternation of physical properties of porphyrin subunits, 2) ethynyl-group bridged porphyrin arrays that are relatively easy to make by palladium-catalyzed reactions display significant changes in their optical and electrochemical properties particularly when the ethynyl groups are attached at the meso-positions of porphyrins, and 3) meso-meso linked multiporphyrin arrays are promising in view of their unique optical properties, easy extension to higher oligomers, and relatively high solubility.
著者
及川 雅人 塚本 俊太郎 諸熊 賢治 入江 樂 生駒 実
出版者
公益社団法人 有機合成化学協会
雑誌
有機合成化学協会誌 (ISSN:00379980)
巻号頁・発行日
vol.78, no.4, pp.292-303, 2020-04-01 (Released:2020-04-08)
参考文献数
70
被引用文献数
1

By a hybrid design of naturally derived excitatory amino acids, dysiherbaines and kainic acid, we have successfully developed a series of artificial glutamate analogs with sp3-rich scaffold via domino Ugi/Diels-Alder reaction, and domino metathesis reaction of oxanorbornenes as key steps. All of the first-generation analogs were found to be neuronally active upon mice intracerebroventricular injection. As the second-generation analogs, we then synthetically modified the heterotricyclic structure, and found that analogs with a carbonyl group on the A-ring still keep the original activity of the first-generation analogs. Structural modification of the second-generation analogs by diversity-oriented reactions such as multicomponent Prins-Ritter reaction was furthermore studied to improve the activity profiles. Electrophysiological studies have identified IKM-159 of the second-generation analogs as an antagonist selective to AMPA-type ionotropic glutamate receptor. The molecular interactions were clarified from crystallographic studies of IKM-159 in complex with GluA2 ligand-binding domain (LBD). From the structure-activity relationships and the structural insights of the complex, a new structural design is proposed herein for neuronally active agents with improved potency and selectivity. We also propose here that generation of sp3-rich scaffold by hybrid strategy of known bioactive molecules would be of use for discovery of artificial bioactive agents with novel activity profiles.
著者
近藤 忠雄 上田 実 吉田 久美
出版者
The Society of Synthetic Organic Chemistry, Japan
雑誌
有機合成化学協会誌 (ISSN:00379980)
巻号頁・発行日
vol.54, no.1, pp.42-53, 1996-01-01 (Released:2009-11-16)
参考文献数
29
被引用文献数
1 4

Various flower colors are in great part due to anthocyanins. Recently, we have elucidated two new mechanisms for blue flower color development on blue cornflower and blue morning glory. The composition of protocyanin, a blue pigment from cornflower, Centaurea cyanus, was determined to consist of six molecules of succinylcyanins (Sucy), six molecules of malonylflavones (Mafl), one ferric ion and one magnesium ion, [Sucy6Mafl6Fe3+Mg2+]. The blue color of protocyanin was due to the LMCT (Ligand to Metal Charge Transfer) interaction between Sucy and Fe3+. The structure of protocyanin was examined by using Al, Mg-protocyanin. The gross structure is much similar to that of commelinin. The pigment of blue morning glory, Ipomoea tricolor, is an triacylated anthocyanin, HBA. We measured the vacuoler pH of the petal of morning glory by using a proton selective micro electrode. The pHv of the petal of purplish red bud was 6.6 and that of blue open flower petal was 7.7. The anhydrobase anion of HBA must be stabilized by intramolecular stacking. We could solve 80 year's problems, one is about cornflower's pigment and the other is the evidence of the pH theory. In both cases hydrophobic interaction followed by formation of supra-molecule is the key of stabilization of anthocyanidin chromophore.
著者
安倍 学
出版者
公益社団法人 有機合成化学協会
雑誌
有機合成化学協会誌 (ISSN:00379980)
巻号頁・発行日
vol.77, no.5, pp.503-511, 2019-05-01 (Released:2019-05-13)
参考文献数
36

Localized singlet diradicals are key intermediates in bond-homolyses. Thorough studies of the reactive species are essential to clarify the mechanisms of the homolytic bond-cleavage and -formation processes. In general, the singlet diradicals are quite short-lived due to the fast radical-radical coupling reactions. The short-lived characteristic has retarded the thorough study on bond-homolyses. In the last two decades, the author and his research group have enjoyed conducting fundamental studies of generating spectroscopically detectable singlet diradicals to clarify the chemistry of localized singlet diradicals. Recently, a new series of long-lived singlet diradicals, viz. 1,2-diazacyclopentane-3,5-diyl and singlet diradical having macrocyclic structures, have been identified, and their electronic structures and novel reactivities were thoroughly studied using laser-flash photolysis (LFP), product analysis, emission analyses, and computational studies. During the research study, two new concepts in chemistry have emerged; (1) π-single bonding (C-π-C) and (2) the third isomer in bond-homolysis processes, i.e. puckered singlet diradicals. This article describes first a short history of localized diradicals, then, the nitrogen-atom effect on the reactivity of singlet diradicals, the chemistry of π-single bonded species, the stereoselectivity in the photochemical denitrogenation reactions, and the adiabatic bond-homolysis process in the electronically excited states.
著者
上田 将史
出版者
公益社団法人 有機合成化学協会
雑誌
有機合成化学協会誌 (ISSN:00379980)
巻号頁・発行日
vol.77, no.7, pp.718-719, 2019-07-01 (Released:2019-07-08)
参考文献数
9

Diarylsulfides are an important class of natural products, pharmaceutical, and functionalized molecules in various research fields such as biology, pharmacy, and material science. However, C-S bond formation reaction is often required high-temperature condition using transition metal catalysts. The appropriate substrate scope is also limited. Therefore, the development of sustainable and efficient procedures for the C-S bond formation is essential in synthetic chemistry. Herein, novel methods for the C-S coupling reaction of diarylsulfides are introduced.
著者
大沢 映二
出版者
The Society of Synthetic Organic Chemistry, Japan
雑誌
有機合成化学協会誌 (ISSN:00379980)
巻号頁・発行日
vol.45, no.11, pp.1033-1043, 1987-11-01 (Released:2009-11-13)
参考文献数
94
被引用文献数
1 1

日本化学会の将来構想委員会が最近公表した報告の中に「化学におけるコンピュータの役割」と題する一章があり,その中で次のように言っている:『(コンピュータ)の役割は今後益々増え(続け),化学の将来に最も重要な分野の一つはコンピュータによる理論的な計算や論理,考察であろう』。コンピュータに向く理論計算法は大きく分けて量子化学計算と分子力学計算である。前者については本特集では別に取り上げられている。後者は一口で言えば分子模型のコンピュータ化であって,特に有機立体化学や有機合成化学への応用に適している。分子力学法の使い方や応用例については本特集では別に解説されるので,ここでは応用に入る前の導入部として,基本的な考え方や今後の動向に重きを置いて纏めてみた。
著者
長瀬 博 松本 和久 西山 久雄
出版者
The Society of Synthetic Organic Chemistry, Japan
雑誌
有機合成化学協会誌 (ISSN:00379980)
巻号頁・発行日
vol.54, no.12, pp.1055-1066, 1996-12-01 (Released:2009-11-16)
参考文献数
44
被引用文献数
6 10

Just after the discovery of PGI2, we started to find chemically and metabolically stable PGI2 derivatives with longer duration of action. Extensive studies led us to a new class of stable PGI2 analogue, 5, 6, 7-trinor-4, 8-inter-m-phenylenePGI2 that has a phenol moiety instead of enol-ether linkage in PGI2. In order to accomplish synthesis of the m-phenylenePGI2, novel synthetic methods were developed, for instance, ortho-selective metal-halogen exchange reaction of bromoanisoles by means of Grignard reagent, copper-catalyzed SN2' cyclization to prepare dihydrocyclopenta [b] benzofuran, and regioselective and stereo-selective elongation of ω-side chain by Prins reaction. Further efforts were devoted to synthesize derivatives of m-phenylenePGI2 with enhanced pharmacological activity and less adverse reaction. Finally, we attained to Beraprost sodium which is the first launched drug as an orally active PGI2. This paper will focus on the study of total syntheses of m-phenylenePGI2.
著者
岡 希太郎 原 昭二
出版者
The Society of Synthetic Organic Chemistry, Japan
雑誌
有機合成化学協会誌 (ISSN:00379980)
巻号頁・発行日
vol.37, no.1, pp.25-39, 1979-01-01 (Released:2010-01-22)
参考文献数
105
被引用文献数
1

This review involves the synthetic studies on the salamander alkaloids isolated from an animal venom in the skin gland of Salamandra maculosa Laurenti. Syntheses of three groups of the alkaloids, one with a bicyclo-oxazolidine system, one with a carbinolamine system, and another with a pure 3-aza-A-homo steroid system, are discussed separately. It will be emphasized that the synthetic works described herein made a considerable contribution to the structure analyses of this field of alkaloids and earlier proposed structures based on X-ray and spectroscopic analyses have been changed step by step. Regio and stereospecific syntheses of the alkaloids are mainly discussed in connection with the construction of the bicyclo-oxazolidine system of the major alkaloids and with Beckmann rearrangement of steroid 3-ketoximes for the syntheses of the other alkaloids.
著者
前田 満和
出版者
The Society of Synthetic Organic Chemistry, Japan
雑誌
有機合成化学協会誌 (ISSN:00379980)
巻号頁・発行日
vol.49, no.11, pp.1021-1031, 1991-11-01 (Released:2009-11-16)
参考文献数
54
被引用文献数
1 3

Cisplatin [cis-dichlorodiammineplatinum (II)] has been widely used for clinical cancer chemotherapy though the complex has severe side effect such as renal toxicity. This article is summarized synthetic method, reactivities, and mechanism of action against target molecules of cisplatin. And a part of newly synthesized cisplatin analogs including our liposoluble or water miscible platinum (II) complexes are summarized with their antitumor activities against experimental tumors.
著者
金子 正勝
出版者
The Society of Synthetic Organic Chemistry, Japan
雑誌
有機合成化学協会誌 (ISSN:00379980)
巻号頁・発行日
vol.49, no.11, pp.989-1001, 1991-11-01 (Released:2009-11-16)
参考文献数
87
被引用文献数
3 8

Recent development in the synthetic chemistry of the antitumor antimetabolites of nucleic acid related compounds has been reviewed. In addition to the methodology of the synthesis of antimetabolites from the point of synthetic chemistry, the antitumor activities and the mechanisms of them have also been mentioned.