Journal of Synthetic Organic Chemistry, Japan
Online ISSN : 1883-6526
Print ISSN : 0037-9980
ISSN-L : 0037-9980
Electro-Organic Synthesis
  • Published: October 01, 2024      Updated: October 01, 2024

Displaying 1-18 of 18 articles
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  • Volume 37 (1979) Issue 5 Pages 372-391      Published: October 01, 2024
    Application of Characteristic Electroreactions to Organic Syntheses
    Tsutomu NONAKA, Toshio FUCHIGAMI
    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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  • Volume 40 (1982) Issue 11 Pages 986-990      Published: October 01, 2024
    Electroorganic Chemistry in Organic Synthesis
    Tatsuya SHONO
    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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  • Volume 43 (1985) Issue 6 Pages 557-564      Published: October 01, 2024
    Electrogenerated Acid (EGA) Catalyzed Reaction
    Kenji UNEYAMA
    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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  • Volume 43 (1985) Issue 6 Pages 583-593      Published: October 01, 2024
    Biomimetic Synthesis of Bioactive Lignans and Neolignans by Means of Electrochemical Method
    Shosuke YAMAMURA
    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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  • Volume 43 (1985) Issue 6 Pages 617-633      Published: October 01, 2024
    Experimental Methods for Electroorganic Synthesis in a Laboratory
    Ikuzo NISHIGUCHI
    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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  • Volume 49 (1991) Issue 9 Pages 798-808      Published: October 01, 2024
    Industrial Electroorganic Synthesis in Europe
    Fritz BECK, Hiroshi SUGINOME
    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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  • Volume 46 (1988) Issue 6 Pages 586-595      Published: October 01, 2024
    New Synthetic Methodologies Involving Electron Transfer Process
    Jun-ichi YOSHIDA
    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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  • Volume 56 (1998) Issue 9 Pages 725-735      Published: October 01, 2024
    The Application of Electroorganic Chemical Reaction
    Shojiro MAKI, Haruki NIWA
    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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  • Volume 64 (2006) Issue 4 Pages 406-414      Published: October 01, 2024
    Environmentally Friendly Electroorganic Synthesis Using Solid-Supported Acids and Bases
    Toshiki Tajima, Toshio Fuchigami
    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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  • Volume 64 (2006) Issue 10 Pages 1010-1020      Published: October 01, 2024
    Organic Synthesis Using Carbocations Generated by Electron Transfer Reactions
    Seiji Suga
    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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  • Volume 69 (2011) Issue 4 Pages 360-369      Published: October 01, 2024
    Metal Catalyzed Redox Reactions of Small Inorganic and Organic Molecules Aimed at Energy Conversion
    Koji Tanaka
    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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  • Volume 70 (2012) Issue 6 Pages 606-614      Published: October 01, 2024
    Molecular Conversion of Conjugated Polymers via Electron-Transfer on Electrode as a Key Step
    Shinsuke Inagi, Toshio Fuchigami
    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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  • Volume 70 (2012) Issue 7 Pages 701-710      Published: October 01, 2024
    Intermolecular Olefin Cross-Metathesis Initiated by the Umpolung of Enol Ethers
    Yohei Okada, Kazuhiro Chiba
    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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  • Volume 72 (2014) Issue 5 Pages 506-517      Published: October 01, 2024
    Development of Novel Organic Electrosynthetic Processes Utilizing Electrochemical Microreactor
    Tsuneo Kashiwagi, Mahito Atobe
    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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  • Volume 72 (2014) Issue 10 Pages 1120-1130      Published: October 01, 2024
    Alkaloid Synthesis by Means of Hypervalent Iodobenzene
    Tsuyoshi Saitoh, Shigeru Nishiyama
    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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  • Volume 73 (2015) Issue 2 Pages 171-180      Published: October 01, 2024
    Development of Cross-Coupling Reactions Including Electro-oxidative Processes and Their Applications to the Synthesis of π-Extended Compounds
    Koichi Mitsudo, Hideo Tanaka, Seiji Suga
    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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  • Volume 79 (2021) Issue 9 Pages 839-848      Published: October 01, 2024
    Synthesis of Oligosaccharides of Glucosamine by Automated Electrochemical Assembly
    Kumpei Yano, Norihiko Sasaki, Toshiyuki Itoh, Toshiki Nokami

    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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  • Volume 82 (2024) Issue 1 Pages 68-78      Published: October 01, 2024
    Designing Electrolysis Sites for Electroorganic Synthesis
    Sigeru Torii
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