有機合成化学協会誌
Online ISSN : 1883-6526
Print ISSN : 0037-9980
ISSN-L : 0037-9980
有機電解反応/合成
  • 公開日: 2024/10/01      更新日: 2024/10/01

    近年、飛躍的に発展している有機電解合成の分野では、長きに渡り日本はその基礎の構築に貢献してきました。協会誌創刊後間もない時期から現在までの多くの研究者の多方面に渡る活躍をご堪能ください。
    （編者一同）

18件中1～18件の論文を表示しています
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  • 37 巻 (1979) 5 号 p. 372-391      公開日: 2024/10/01
    特徴的な電解反応の有機合成への応用
    野中 勉, 渕上 寿雄
    This review is organized under the following headings with 440 references.
    1. Generation and reactions of reactive intermediates.
    1.1. Carbon species. 1.2. Nitrogen species. 1.3. Oxygen species. 1.4. Others.
    2. Reactions of organic hetero atoms.
    2.1. Nitrogen. 2.2. Sulfur. 2.3. Phosphorus and others.
    3. Formation and reactions of organometallic compounds.
    3.1. Formation of metallic compounds employing electrodes as a metal source.
    3.2. Conversion of metallic compounds to other metallic compounds. 3.3. Formation of nonmetallic compounds from metallic compounds.
    4. Bimolecular reactions.
    4.1. Dimerization. 4.2. Cyclization. 4.3. Ring expansion and contraction.
    5. Stereochemistry.
    5.1. Stereoselective and stereospecific reactions. 5.2. Asymmetric reactions and asymmetric syntheses.
    6. New type reactions.
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  • 40 巻 (1982) 11 号 p. 986-990      公開日: 2024/10/01
    エレクトロオーガニックケミストリーと有機合成
    庄野 達哉
    The past and the present of the electroorganic chemistry have been described from the standpoints of organic synthesis and industrial application.
    Three typical characteristics of the electroorganic chemistry, that is, umpolung, nature of electrified interface, and mediator have been briefly explained, and the future of the electroorganic chemistry has been viewed from these three aspects.
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  • 43 巻 (1985) 6 号 p. 557-564      公開日: 2024/10/01
    電解系酸触媒反応
    宇根山 健治
    This review summarizes : (1) electrolysis conditions useful for the effective generation of electrogenerated acid (EGA), (2) discussion on the generation mechanism of EGA, and (3) the recently developed EGA-catalyzed reactions for the selective organic functional group transformation.
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  • 43 巻 (1985) 6 号 p. 583-593      公開日: 2024/10/01
    電極反応を利用した生理活性リグナンおよびネオリグナン類の合成
    山村 庄亮
    From a biogenetic point of view, a number of bioactive lignans and neolignans formed by the oxidative dimerization of various C6-C3 units are regio- and stereo-selectively synthesized using electrochemical method, in which anodic oxidation of the corresponding phenols as a key-step is carried out under various conditions. Particularly, a simple method leading to the formation of bicyclo [3. 2. 1] octanones is demonstrated.
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  • 43 巻 (1985) 6 号 p. 617-633      公開日: 2024/10/01
    実験室における有機電極合成の実際
    西口 郁三
    This article contains a variety of laboratory-scale experimental methods for electroorganic synthesis, which may probably give practical guidelines or some clues to a synthetic organic chemist who has not been famililar with this specific but useful technique in organic synthesis in spite of his much interest.
    Following items are explained mainly in order to seek good answers for many problems, such as how to get easy availability of equipment, simplicity of procedure, solution of various experimetal trouble and optimum reaction conditions.
    1) Preface
    2) Equipment to prepare.
    3) Various type of methods and practical examples of electroorganic synthesis.
    4) Experimental factors controlling electroorganic reaction -Searching of optimum reaction conditions-
    5) Final comment
    As this specific reaction may be generally controlled by more experimental factors than ordinary chemical reaction in solution, more “try and error” may be required to get optimum conditions, hopefully, by simpler equipment and procedure.
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  • 49 巻 (1991) 9 号 p. 798-808      公開日: 2024/10/01
    ヨーロッパにおける有機電解合成工業
    Fritz BECK, 杉野目 浩
    Industrial electrosynthesis of organics in Europe is comprehensively treated. The products are divided in ten classes. Besides the adiponitrile process in UK, the sebacic acid process in USSR and the benzaldehyde process in Germany, scaled up to at least 1, 000 tons per year, numerous small capacity processes are described. Undivided cells are employed with increasing tendency.
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  • 46 巻 (1988) 6 号 p. 586-595      公開日: 2024/10/01
    電子移動過程を基礎概念とする新しい有機合成
    吉田 潤一
    The following new synthetic methodologies involving electron transfer process have been developed. (1) Cleavage of the carbon-silicon bond : The carbon-silicon bonds in organopentafluorosilicates are cleaved by various oxidizing agents via initial electron transfer. The carbon-silicon bonds in allylsilanes and α-heteroatom substituted organosilicon compounds are also cleaved by electrochemical oxidation. (2) Indirect electrochemical oxidation using polymeric electron carrier such as poly (vinylpyridinium) bromide. (3) Cycloaddition of 1, 3-dicarbonyl compounds : The radical species generated by electrochemical oxidation of 1, 3-diketones adds to the olefin to give the formal [3 + 2] cycloadducts, dihydrofurans or tetrahydrofurans. In the presence of molecular oxygen the formal [2 + 2 + 2] cycloaddition of 1, 3-diketone, olefin and molecular oxygen takes place. The electroinitiated radical chain mechanism is proposed.
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  • 56 巻 (1998) 9 号 p. 725-735      公開日: 2024/10/01
    有機合成における電極反応の応用
    牧 昌次郎, 丹羽 治樹
    The chemical, site-specific oxidations of saturated hydrocarbons as mimic for biological process are important subjects in synthetic organic chemistry. Such oxidations are seldom achieved in conventional chemistry. The development of such methodology is challenging, extensive studies which are currently ongoing in many laboratories. Recently we found that the electrochemical oxidation can achieve the site-specific hydroxylation of a certain inactivated methine and methylene groups in moderate or good yields. Further we achieved stereoselective chlorination of steroidal double bonds and selective cleavage of styrylic olefins as well as the triene of vitamin D2 by electrolysis. Descried herein are the scope and limitation, and the synthetic application of such electrochemical oxidation reactions.
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  • 64 巻 (2006) 4 号 p. 406-414      公開日: 2024/10/01
    固体酸・固体塩基を用いる環境調和型有機電解合成
    田嶋 稔樹, 淵上 寿雄
    We have successfully developed novel electrolytic systems using solid-supported acids and bases. Anodic fluorination of various compounds using KF as a fluorine source and solid-supported acids as a supporting electrolyte was successfully carried out to provide the corresponding fluorinated products in good to excellent yields. On the other hand, anodic methoxylation, anodic acetoxylation, Kolbe electrolysis, and non-Kolbe electrolysis of various compounds using solid-supported bases as a precursor of supporting electrolytes were also conducted to afford the corresponding methoxylated, acetoxylated, Kolbe, and non-Kolbe products in moderate to excellent yields, respectively.
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  • 64 巻 (2006) 10 号 p. 1010-1020      公開日: 2024/10/01
    電子移動反応による炭素カチオンの創製を機軸とする新しい有機合成
    菅 誠治
    We have developed the “cation pool” method in which carbocations such as alkoxycarbenium ions and N-acyliminium ions are generated and accumulated in conventional reaction media by low temperature electrochemical oxidation. The carbocations thus produced are allowed to react with a variety of nucleophiles. Various organic transformations using the cation pool method, such as reductive radical couplings, cationic carbohydroxylations, three-component couplings, and additions of organic radicals, have also been developed. Combinatorial sequential synthesis using the “cation flow” method, in which carbocations are generated in an electrochemical microflow system, has been achieved as well.
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  • 69 巻 (2011) 4 号 p. 360-369      公開日: 2024/10/01
    エネルギー変換を目指した錯体触媒による無機および有機小分子の酸化還元反応の開発
    田中 晃二
    An aqua-Ru-quinone complex, [Ru(trpy)(Q)(OH2)]2+ (trpy=2,2’: 6’,2”-terpyridine, Q=3,5-di-tert-butyl-1,2-benzoquinone, or 3,6-di-tert-butyl-1,2-benzoquinone) dissociates two protons in a stepwise fashion. The pKavalues of [Ru(trpy)(Q)(OH2)]+ and [Ru(trpy)(Q)(OH)]+ are 5.5 and 10.5, respectively. Proton dissociation of the latter is coupled with electron transfer from the resultant O2− to Q to produce an unusual O-radical complex, [Ru(trpy)(Sq)(O−·)]0 (Sq=3,5-di-tert-butyl-1,2-benzosemiquinone). Dissociation of an amino proton of analogous [Ru(trpy)(Q)(NH3)]2+ (pKa6.2) results in similar intramolecular electron transfer from NH2− to Q with generating an N-radical complex, [Ru(trpy)(Sq)(NH2·)]+. One-electron oxidation of [Ru(trpy)(Sq)(NH2·)]2+ produces [Ru(trpy)(Q)(NH2·)]2+, which reacts with alcohols to give the correspondent aldehyde or ketone with regeneration of [Ru(trpy)(Sq)(NH3)]+. On the other hand, two electron oxidation of [Ru(trpy)(Sq)(O−·)]0 generates a catalytic ability to oxidize alcohols. The catalytic activity of the O-radical complex is less than that of N-radical one. Dinuclear Ru complexes bridged with an anthracene framework, [Ru2(btpyan)(Q)2(OH)2]2+ and [Ru2(btpyan)(bpy)2(OH)2]2+ (btpyan=1,8-bis(2,2’: 6’,2”-terpyrid-4’-yl)anthracene) catalyze four-electron oxidation of water. The catalytic activity for O2 production by [Ru2(btpyan)(Q)2(OH)2]2+ is much higher than [Ru2(btpyan)(bpy)2(OH)2]2+. Proton dissociation of [Ru2(btpyan)(Q)2(OH)2]2+ spontaneously produces [Ru2(btpyan)(Sq)2(O−·)2]0, and the subsequent oxidation of the two Ru(Sq)(O−·) groups induces O-O bond formation through the coupling reaction of two O-radicals. On the other hand, deprotonation of [Ru2(btpyan)(bpy)2(OH)2]2+ is caused by oxidation of [Ru2(btpyan)(bpy)2(OH)2]2+, and four electron oxidation affords [RuIV2(btpyan)(bpy)2(=O)2]4+ without passing through an O-radical complex. High catalytic activity of [Ru2(btpyan)(Q)2(OH)2]2+ compared with [Ru2(btpyan)(bpy)2(OH)2]2+ as to the O2 evolution is associated with the easiness of the O-O bond formation by the coupling reaction of two Ru-O· radicals compared with that of two RuIV=O groups. A new pbn (pbn=2-pyridylbenzo[b]-1,5-naphthyridine) ligand was designed to simulate the NAD+/NADH redox reaction as a possible renewable hydride donor. A series of [Ru(bpy)3−n(pbn)n]2+ (n=1, 2, 3) complexes undergoes photo-induced two-(n=1), four-(n=2), and six-electron reductions (n=3) under irradiation of visible light in the presence of N(CH2CH2OH)3.
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  • 70 巻 (2012) 6 号 p. 606-614      公開日: 2024/10/01
    電極電子移動をキーステップとする共役系高分子の分子変換
    稲木 信介, 淵上 寿雄
    Electron-transfer behaviors of conjugated polymers on electrode (electrochemical doping) have been studied well for the purpose of electrochemical device applications such as conducting material and electrochromic material. In this study, we treated a charged (doped) state of conjugated polymers as an intermediate for following chemical reactions based on the concept of electroorganic synthesis. The post-functionalization of conjugated polymers was successfully achieved when a reactive dopant (conter ion derived from electrolyte) was used for the electrochemical reactions. For example, the polymer reactions such as anodic halogenations, cathodic reduction, and gradient oxidation reaction on bipolar electrode were successfully carried out to tune the optical and electrochemical properties of the polymers.
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  • 70 巻 (2012) 7 号 p. 701-710      公開日: 2024/10/01
    エノールエーテルの極性転換によって開始される分子間オレフィンクロスメタセシス
    岡田 洋平, 千葉 一裕
    Electrochemical approaches have proven to be effective for regulating either one or two electron transfers at the surface of the electrodes that afford not only various functional group transformations, but also a wide variety of carbon-carbon bond forming reactions. Especially, the anodic oxidation of electron-rich olefins generates their radical cations, which are then trapped by a variety of nucleophiles, leading to a number of interesting cyclizations. These anodic transformations are initiated by the umpolung processes that normally nucleophilic electron-rich olefins are anodically oxidized to give electrophilic radical cations to react with second nucleophiles. Meanwhile, unactivated olefins have been found to act as carbon nucleophiles in lithium perchlorate/nitromethane electrolyte solutions that can be used to construct intermolecular carbon-carbon bonds. The use of enol ethers as electron-rich olefins has led to the formation of cyclobutane-like intermediates through which intermolecular olefin cross-coupling and -metathesis are achieved.
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  • 72 巻 (2014) 5 号 p. 506-517      公開日: 2024/10/01
    電気化学マイクロリアクターを活用する新規有機電解合成プロセスの開発
    柏木 恒雄, 跡部 真人
    Electron transfer is one of the most typical driving factors for organic reaction, and organic electrosynthesis serves as a straightforward and powerful method for organic electron transfer processes. On the other hand, microreactor technology for organic synthesis has been significantly investigated for the past two decades, however, the integrated use of microreactor technology with organic electrosynthesis has been quite limited so far. We report here that the integrated use of microreactor technology with organic electrosynthesis which offers one of the most sophisticated processes in organic chemistry. In particular, (a) Organic electrosynthetic processes without using intentionally added supporting electrolyte, (b) Organic electrosynthetic processes utilizing liquid-liquid parallel laminar flow, (c) Novel paired electrolytic processes, and (d) Multi-step reaction systems via electrogenerated species, have been described.
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  • 72 巻 (2014) 10 号 p. 1120-1130      公開日: 2024/10/01
    超原子価ヨードベンゼンを活用した含窒素天然物の合成
    斉藤 毅, 西山 繁
    The novel organic iodine (III) reagent, phenyliodine bis(trifluoroethoxide) (PIFE), was developed by means of electrochemical oxidation process from iodobenzene. PIFE showed the great reactivity against amide derivatives such as methoxy and acyl anilide as well as commercially available organic iodine (III) reagents, and pH of its reaction media was almost neutral. The oxidative syntheses of azaspirodienone and quinolinone through the nitrenium ion were successfully achieved with PIFE. Moreover, oxidative ring closing reaction of biaryl acetoanilide was also achieved with PIFE not the presence of transition metal catalyst and provided several carbazole derivatives. During the course of our exploratory research for the scope and limitation of oxidative ring formation with PIFE, the authors developed the novel pyrolidinoindoline synthetic method by means of organic iodine (III) reagents.
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  • 73 巻 (2015) 2 号 p. 171-180      公開日: 2024/10/01
    電気化学的な酸化プロセスを含むカップリング反応の開発と拡張π電子系化合物合成への応用
    光藤 耕一, 田中 秀雄, 菅 誠治
    An electrochemical method to synthesize cationic palladium complexes has been developed. Their counter anions could be changed readily by the electrolyte. The reaction could be incorporated into electro-oxidative palladium catalyzed reactions, such as Wacker-type reaction, homo-coupling of arylboronic acids, oxidative Sonogashira-type coupling, and Glaser-type coupling of terminal alkynes. These reactions exhibited a wide scope and a variety of products were obtained in high yields due to high activity of electrogenerated palladium species. We also developed site-selective sequential reactions by the integration of the electro-oxidative coupling reactions with non-electrochemical reactions. The reaction site could be controlled completely by the on/off application of electricity.
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  • 79 巻 (2021) 9 号 p. 839-848      公開日: 2024/10/01
    液相電解自動合成によるオリゴグルコサミンの合成
    矢野 君晟, 佐々木 紀彦, 伊藤 敏幸, 野上 敏材

    The automated electrochemical assembly is one of our arrial points for development of electrochemical methods for oligosaccharide synthesis. The one-pot sequential process of activation of thioglycoside building block by electrochemical oxidation and coupling with thioglycoside building block can be carried out in automated manner, and muliple cycles of the process enables us to synthesis oligosaccharides with desired chain length. We have synthesized oligoglucosamines with β-1,6- and β-1,4-glycosidic linkages. Total synthesis of TMG-chitotriomycin and Myc-IV (C16 : 0, S), which are biologically active oligoglucosamines derivatives, has also achieved. Ionic liquid tags were introduced to glucosamine building blocks to facilitate separation of products; however, they worked not only separation tag but also electrolyte and stereo-controlling group in electrochemical glycosylation. We also found that electrochemical glycosylation was also useful to convert linear oligosaccharides of glucosamines into the corresponding cyclic oligosaccharides.
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  • 82 巻 (2024) 1 号 p. 68-78      公開日: 2024/10/01
    有機電解合成を主軸とする有機合成の展開
    鳥居 滋
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