基本情報

所属

• 工学研究院　応用化学部門　有機工業化学分野

職名

• 准教授

学位

• 博士（工学）（北海道大学）

ORCID ID

•  https://orcid.org/0000-0003-2205-626X

J-Global ID

• 200901044901395492

研究キーワード

• 有機ラジカル反応   有機電気化学   有機合成化学   Organic Radical Reaction   Electroorganic Chemistry   Synthetic Organic Chemistry   

研究分野

• ナノテク・材料 / 有機合成化学

担当教育組織

•  学士課程　工学部
•  修士課程　総合化学院
•  博士課程　総合化学院

職歴

• 2017年10月 - 現在 放送大学 非常勤講師
• 2010年04月 - 現在 北海道大学大学院総合化学院 准教授（兼務）
• 2010年04月 - 現在 北海道大学大学院工学研究院 准教授
• 2019年06月 - 2019年06月 近畿大学 大学院理工学研究科 非常勤講師
• 2018年07月 - 2018年09月 お茶の水女子大学 大学院人間文化創成科学研究科 非常勤講師
• 2007年04月 - 2010年03月 北海道大学大学院工学研究科 准教授
• 2002年04月 - 2007年03月 北海道大学大学院工学研究科 助教授
• 2003年10月 - 2004年07月 カナダ・トロント大学 客員教授
• 1997年04月 - 2002年03月 北海道大学大学院工学研究科 助手
• 1994年06月 - 1997年03月 北海道大学工学部分子化学専攻 助手
• 1992年05月 - 1994年06月 北海道大学工学部合成化学工学科 助手

学歴

•         - 1992年09月   北海道大学   博士（工学）
•         - 1992年03月   北海道大学   大学院工学研究科   合成化学工学専攻博士課程 単位取得退学
•         - 1989年03月   北海道大学   大学院工学研究科   合成化学工学専攻修士課程 修了
•         - 1987年03月   北海道大学   工学部   合成化学工学科 卒業

所属学協会

• 有機電子移動化学研究会   日本フッ素化学会   有機合成化学協会   電気化学会   日本化学会   The Society of Synthetic Organic Chemistry, Japan   The Electrochemical Society of Japan   The Chemical Society of Japan   

研究活動情報

論文

• Synthesis of Carboxylic Acid by Electrochemical Fixation of Carbon Dioxide: A Review of Electrochemical Carboxylation from Past to Latest

  Hisanori Senboku

  Current Organic Chemistry 2024年01月
• N-methyldiethanolamine (MDEA) as an effective CO2 absorbent for direct air capture (DAC) in cement-based materials

  Kirushnapillai Kopitha, Elakneswaran Yogarajah, Ryoma Kitagaki, Ryosuke Saito, Masato Tsujino, Akira Nishida, Hisanori Senboku, Naoki Hiroyoshi

  Chemical Engineering Journal 2023年11月
• Direct Substitution of a Hydroxyl Group by a Carboxyl Group at the Benzylic Position in Benzyl Alcohols by Electrochemical Reduction in the Presence of Carbon Dioxide: Improvement Enabling Electrochemical Direct Carboxylation of Benzyl Alcohols even in the Absence of an Electron-withdrawing Group on the Phenyl Ring

  Mizuki HAYAMA, Hisanori SENBOKU

  Electrochemistry 2023年
• Electrochemical Friedel–Crafts-type amidomethylation of arenes by a novel electrochemical oxidation system using a quasi-divided cell and trialkylammonium tetrafluoroborate

  Hisanori Senboku, Mizuki Hayama, Hidetoshi Matsuno

  Beilstein Journal of Organic Chemistry 2022年08月18日
• Synthesis of N-Boc-α-amino Acids from Carbon Dioxide by Electrochemical Carboxylation of N-Boc-α-aminosulfones

  Hisanori Senboku, Yoshihito Minemura, Yuto Suzuki, Hidetoshi Matsuno, Mayu Takakuwa

  The Journal of Organic Chemistry 2021年09月22日 [査読有り][招待有り]
  
• Electrochemical Fixation of Carbon Dioxide: Synthesis of Carboxylic Acids

  H. Senboku

  The Chemical Record 21 9 2354 - 2374 2021年09月 [査読有り]
  
• Integrated Flow Synthesis of α-Amino Acids by In Situ Generation of Aldimines and Subsequent Electrochemical Carboxylation

  Yuki Naito, Yuto Nakamura, Naoki Shida, Hisanori Senboku, Kenta Tanaka, Mahito Atobe

  The Journal of Organic Chemistry 2021年06月21日 [査読有り]
  
• Synthesis of indolo[2,1‐a]isoquinolines by CF3COOH‐induced cyclization

  Yasuhiro Wada, Nobuhito Kurono, Hisanori Senboku, Kazuhiko Orito

  Journal of Heterocyclic Chemistry 57 10 3703 - 3708 2020年10月 [査読有り][通常論文]
   

  Indolo[2,1-a]isoquinoline alkaloids and related compounds have been known to have interesting biological activities, such as antileukemic and antitumor activities. We found that 1-(3,4-dimethoxyphenethyl)indole gave 2,3-dimethoxyindolo[2,1-a]isoquinoline and 1-(3,4-dimethoxyphenylacetyl)indole gave 2,3-dimethoxy-6-oxoindolo[2,1-a]isoquinoline, respectively, by an intramolecular cyclization carried out in boiling trifluoroacetic acid.
• Efficient Synthesis of Mandel Acetates by Electrochemical Carboxylation of Benzal Diacetates

  Senboku Hisanori, Sakai Kanae, Fukui Akihiro, Sato Yusuke, Yamauchi Yusuke

  ChemElectroChem (IF: 3.975) 5 16 4158 - 4164 2019年03月 [査読有り][通常論文]
  
• Bioinspired synthesis of pentalene-based chromophores from an oligoketone chain

  Yuki Saito, Masayuki Higuchi, Shota Yoshioka, Hisanori Senboku, Yasuhide Inokuma

  Chemical Communications 54 50 6788 - 6791 2018年 [査読有り][通常論文]
   

  We report a bioinspired synthesis of 2,5-dihydropentalene-based chromophores from an aliphatic oligoketone bearing 1,3- and 1,4-diketone subunits. Unlike the natural polyketone sequence, fused five-membered rings were formed via an intramolecular aldol condensation. A subsequent Knoevenagel condensation reaction with malononitrile furnished a multiply cross-conjugated π-system with low-lying LUMO levels. Furthermore, pentalenes obtained from a non-conjugated aliphatic chain exhibited visible absorption and solid-state fluorescence.
• Electrochemical carboxylation with carbon dioxide

  Hisanori Senboku, Asahi Katayama

  Current Opinion in Green and Sustainable Chemistry 3 50 - 54 2017年02月01日 [査読有り][通常論文]
   

  Studies carried out in the past two years on electrochemical fixation of carbon dioxide with carbon-carbon bond formation, so-called electrochemical carboxylation or electrocarboxylation, are reviewed. Among about twenty papers on electrochemical carboxylation published from 2014 to the present, recent advances in electrochemical carboxylation regarding asymmetric carboxylation, sacrificial anode-free carboxylation, and carboxylation following aryl radical cyclization are focused on and discussed.
• Sequential Vinyl Radical Cyclization/Fixation of Carbon Dioxide through Electrochemical Reduction of Vinyl Bromide in the Presence of an Electron-Transfer Mediator

  Asahi Katayama, Hisanori Senboku

  CHEMELECTROCHEM 3 12 2052 - 2057 2016年12月 [査読有り][通常論文]
   

  Constant-current electrolysis of vinyl bromide in DMF containing 0.1m Bu4NBF4 by using an undivided cell equipped with a platinum plate cathode and a magnesium rod anode in the presence of an electron-transfer mediator, methyl 4-tert-butylbenzoate, and carbon dioxide resulted in selective generation of a vinyl radical, for which cyclization followed by fixation of carbon dioxide with a carbon-carbon bond formation gave ,-unsaturated carbo- and heterocycle carboxylic acids in moderate to good yields. The vinyl radical could be selectively generated under the electrolysis conditions, and the following reaction of the anion species, generated by one-electron reduction of the resulting cyclized radical, with carbon dioxide took place efficiently. These results and cyclic voltammetry indicate that methyl 4-tert-butylbenzoate plays an important role in the generation of vinyl radicals from vinyl bromides. The resulting cyclized ,-unsaturated carboxylic acid was successfully applied to stepwise and direct iodo-lactonization to give the corresponding bicycle -lactones in good yields.
• Aryl radical cyclization with alkyne followed by tandem carboxylation in methyl 4-tert-butylbenzoate-mediated electrochemical reduction of 2-(2-propynyloxy)bromobenzenes in the presence of carbon dioxide

  Asahi Katayama, Hisanori Senboku, Shoji Hara

  TETRAHEDRON 72 31 4626 - 4636 2016年08月 [査読有り][通常論文]
   

  Constant current electrolysis of 2-(2-propynyloxy)bromobenzenes in DMF using an undivided cell equipped with a Pt cathode and an Mg anode in the presence of carbon dioxide and an electron transfer mediator, methyl 4-tert-butylbenzoate, resulted in aryl radical cyclization with a carbon carbon triple bond followed by fixation of two molecules of carbon dioxide to give 2,2-ring-fused succinic acid derivatives in moderate to good yields. Dihydrobenzofuran, indoline, dihydrobenzothiophene, and indane as well as tetrahydropyran skeletons were successfully constructed by aryl radical cyclization, and unique tandem carboxylation successively occurred to produce succinic acids. One of the resulting succinic acid derivatives, 3-carboxy-2,3-dihydrobenzofuran-3-ylacetic acid, was successfully applied to the synthesis of a novel spiro compound consisting of 2,3-dihydrobenzofuran and gamma-butyrolactone at each C3 position in two steps in high yield. (C) 2016 Elsevier Ltd. All rights reserved.
• Electrochemical direct carboxylation of benzyl alcohols having an electron-withdrawing group on the phenyl ring: one-step formation of phenylacetic acids from benzyl alcohols under mild conditions

  Hisanori Senboku, Kenji Yoneda, Shoji Hara

  TETRAHEDRON LETTERS 56 48 6772 - 6776 2015年12月 [査読有り][通常論文]
   

  Electrochemical direct carboxylation of benzyl alcohols having an electron-withdrawing group on the phenyl ring was successfully carried out by constant current electrolysis using an undivided cell equipped with a platinum plate cathode and a magnesium rod anode in DMF in the presence of carbon dioxide. Reductive cleavage of the C-O bond followed by fixation of carbon dioxide efficiently took place at the benzylic position without any additive to give the corresponding phenylacetic acids in good yields in one step under neutral and mild conditions. (C) 2015 Elsevier Ltd. All rights reserved.
• Three-component coupling reaction of benzylic halides, carbon dioxide, and N,N-dimethylformamide by using paired electrolysis: sacrificial anode-free efficient electrochemical carboxylation of benzylic halides

  Hisanori Senboku, Kotaro Nagakura, Tsuyoshi Fukuhara, Shoji Hara

  TETRAHEDRON 71 23 3850 - 3856 2015年06月 [査読有り][通常論文]
   

  Sacrificial anode-free efficient electrochemical carboxylation of benzylic halides was successfully performed by using a paired electrolysis protocol. Constant-current electrolysis of a DMF solution of benzylic halides in the presence of carbon dioxide using a one-compartment cell equipped with a Pt plate cathode and a Pt wire anode (quasi-divided cell) resulted in efficient three-component coupling reaction of benzylic halides, carbon dioxide and DMF to yield N-methyl-N-(phenylacetoxy)methylformamides, as carboxylated coupling products, in good yields. (C) 2015 Elsevier Ltd. All rights reserved.
• Electrochemical fixation of CO2 to organohalides in room-temperature ionic liquids under supercritical CO2

  Hiroyuki Tateno, Koji Nakabayashi, Tsuneo Kashiwagi, Hisanori Senboku, Mahito Atobe

  ELECTROCHIMICA ACTA 161 212 - 218 2015年04月 [査読有り][通常論文]
   

  The electrochemical properties of novel reaction media, ionic liquid (IL)/supercritical CO2 (scCO(2)) systems, were evaluated and the electrochemical carboxylation of various organohalides in these systems was demonstrated. Voltammetric studies revealed that the CO2 solubility in an IL such as N, N-diethyl-N-methyl-N-(2-methoxyethyl) ammonium bis(trifluoromethanesulfonyl) imide ([DEME] [TFSI]) increased in the presence of scCO(2). The IL/scCO(2) systems were found to be effective for the electrochemical carboxylation of various organohalides. (C) 2015 Elsevier Ltd. All rights reserved.
• Development of a novel electrochemical carboxylation system using a microreactor

  Hiroyuki Tateno, Yoshimasa Matsumura, Koji Nakabayashi, Hisanori Senboku, Mahito Atobe

  RSC ADVANCES 5 119 98721 - 98723 2015年 [査読無し][通常論文]
   

  We have developed a novel electrochemical carboxylation system for CO2 fixation to benzyl halides using a microreactor. In this system, electrochemical carboxylation of benzyl halides proceeded very efficiently without the use of a sacrificial anode such as a Mg anode to give carboxylated products in excellent yields.
• Regioselective electrochemical carboxylation of polyfluoroarenes

  Hisanori Senboku, Kenji Yoneda, Shoji Hara

  Electrochemistry 81 5 380 - 382 2013年05月 [査読無し][通常論文]
   

  Constant current electrolysis of polyfluoroarenes in DMF containing 0.1 moldm-3 Bu4NBF4 in the presence of carbon dioxide by using a one-compartment cell equipped with a Pt cathode and a Mg anode at -40°C resulted in reductive cleavage of a C-F bond of the phenyl ring followed by reaction with carbon dioxide in highly regio- and chemoselective manners to give the corresponding mono-carboxylated products, polyfluorobenzoic acids, in moderate to good yields.
• Synthesis of 8-Oxoberbines and Related Benzolactams by Pd(OAc)2-Catalyzed Direct Aromatic Carbonylation

  Mamoru Miyazawa, Takashi Tokuhashi, Akiyoshi Horibata, Takatoshi Nakamura, Yu Onozaki, Nobuhito Kurono, Hisanori Senboku, Masao Tokuda, Takeshi Ohkuma, Kazuhiko Orito

  JOURNAL OF HETEROCYCLIC CHEMISTRY 50 E48 - E54 2013年02月 [査読無し][通常論文]
   

  A variety of alkoxy-substituted benzolactams with a berbine or yohimbane skeleton were prepared from 1-benzyl-1,2,3,4-tetrahydroisoquinolines or 1-benzyl-1,2,3,4-tetrahydro-beta-carbolines by a phosphine-free Pd(II)-catalyzed direct aromatic carbonylation in a Pd(OAc)(2)-Cu(OAc)(2) catalytic system. The site selectivity was compared with that of the carbonylation with Pd(OAc)(2) or Pd(OAc)(2)center dot 2 PPh3, respectively.
• Some mechanistic studies on electrochemical carboxylation of flavones to yield flavanone-2-carboxylic acids

  Hisanori Senboku, Yusuke Yamauchi, Natsuko Kobayashi, Akihiro Fukui, Shoji Hara

  ELECTROCHIMICA ACTA 82 450 - 456 2012年11月 [査読有り][通常論文]
   

  Electrochemical carboxylation of flavones was successfully demonstrated. Constant current electrolysis of a DMF solution of flavones containing 0.1 M Bu4NBF4 in the presence of carbon dioxide by using a one-compartment cell equipped with a Pt cathode and an Mg anode at 0 degrees C resulted in fixation of carbon dioxide at the C2-position of flavones in a highly regioselective manner to give flavanone-2-carboxylic acids in moderate to good yields. From the results of some mechanistic examinations, we could conclude that flavanone-2-carboxylic acids were produced through exclusive mono-carboxylation of flavones at the C2-position and that dicarboxylation both at the C2- and C3-positions of flavones hardly proceeded. We report herein details of the electrochemical carboxylation of flavones to obtain flavanone-2-carboxylic acids, and we propose a reaction mechanism for the C2-selective carboxylation. (C) 2012 Elsevier Ltd. All rights reserved.
• Synthesis of Benzo[c]phenanthridine Alkaloids by Pd(OAc)2-Induced Direct Aromatic Carbonylation

  Eri Kumazawa, Takashi Tokuhashi, Akiyoshi Horibata, Nobuhito Kurono, Hisanori Senboku, Masao Tokuda, Takashi Ohkuma, Kazuhiko Orito

  EUROPEAN JOURNAL OF ORGANIC CHEMISTRY 2012 24 4622 - 4633 2012年08月 [査読有り][通常論文]
   

  The Pd(OAc)2-induced carbonylation of alkoxy-substituted 1-amino-2-phenyltetralins and 1-amino-2-phenylnaphthalenes was examined to provide the benzo[c]phenanthridine ring system. The carbonylation of substrates containing methylenedioxy groups gave oxysanguinarine and oxyavicine. The tetramethoxy derivatives gave O-methyloxyfagaronine. The substrate with a benzyloxy group afforded a known synthetic precursor to the antileukemic alkaloid, fagaronine.
• Phosphane-Free Pd-0-Catalyzed Cycloamination and Carbonylation with Pd(OAc)(2) and Cu(OAc)(2) in the Presence of K2CO3: Preparation of Benzocyclic Amines and Benzolactams

  Rika Harada, Naoto Nishida, Shiho Uchiito, Yu Onozaki, Nobuhito Kurono, Hisanori Senboku, Tokuda Masao, Takeshi Ohkuma, Kazuhiko Orito

  EUROPEAN JOURNAL OF ORGANIC CHEMISTRY 2012 2 366 - 379 2012年01月 [査読有り][通常論文]
   

  Phosphane-free Pd-0-catalyzed intramolecular aromatic amination was studied. o-Halophenethylamines and 3-(o-halophenyl)propylamines were found to be transformed into indolines and quinolines in a catalytic system based on Pd(OAc)(2) and Cu(OAc)(2) in the presence of K2CO3. Application of the method to substrates containing isoquinoline rings - the 1-(o-bromobenzyl)-3,4-dihydroisoquinolines 6, the 1-(o-bromobenzyl)-1,2,3,4-tetrahydroisoquinolines 7, and the 1-(o-bromophenethyl)isoquinolines 9 - provided the indolo[2,1-a] isoquinoline and dibenzo[a,f] quinolizine ring systems 8 and 10. Extension of the method to beta-carbolines (compounds 11, 12, and 17) produced the benz[f] indolo[2,3-a]indolizine-13-ones 15 and the benz[f] indolo[2,3-a] quinolizine 18. The benzo[f] pyrido[3,4-a] indolizine and indolo[f] pyrido[ 3,4-a]indolizin-12-one ring systems 27 and 31 were built in a similar manner. It was also found that under an atmosphere of CO the same catalytic system produced the corresponding benzolactams, the isoquino[2,1-a][2,7] naphthyridine 34 and the indolo[2,3-a] pyrido[g]quinolizin-8-one 36 [(+/-)-dihydronauclefine] in good yields.
• Electrochemical Carboxylation of Flavones: Facile Synthesis of Flavanone-2-carboxylic Acids

  Hisanori Senboku, Yusuke Yamauchi, Natsuko Kobayashi, Akihiro Fukui, Shoji Hara

  ELECTROCHEMISTRY 79 11 862 - 864 2011年11月 [査読有り][通常論文]
   

  Constant current electrolysis of flavones in DMF containing 0.1 mol dm(-3) Bu4NBF4 in the presence of CO2 by using a one-compartment cell equipped with a Pt cathode and an Mg anode resulted in reductive carboxylation at the C-2 position of flavones in a highly regioselective manner to give flavanone-2-carboxylic acids in moderate to good yields.
• Facile Synthesis of 2,3-Dihydrobenzofuran-3-ylacetic Acids by Novel Electrochemical Sequential Aryl Radical Cyclization-Carboxylation of 2-Allyloxybromobenzenes Using Methyl 4-tert-Butylbenzoate as an Electron-Transfer Mediator

  Hisanori Senboku, Jun-ya Michinishi, Shoji Hara

  SYNLETT 2011 11 1567 - 1572 2011年07月 [査読有り][通常論文]
   

  Facile synthesis of 2,3-dihydrobenzofuran-3-ylacetic acids and related analogues was successfully carried out by a novel electrochemical aryl radical generation and its 5-exo cyclization followed by a carboxylation sequence of 2-allyloxybromobenzenes by using methyl 4-tert-butylbenzoate as an electron-transfer mediator.
• Electrochemical carboxylation of benzylic carbonates: alternative method for efficient synthesis of arylacetic acids

  Masashi Ohkoshi, Jun-Ya Michinishi, Shoji Hara, Hisanori Senboku

  TETRAHEDRON 66 39 7732 - 7737 2010年09月 [査読有り][通常論文]
   

  Electrochemical carboxylation of benzylic carbonates was successfully performed as an alternative method for the synthesis of phenylacetic acids by using a one-compartment cell equipped with a Pt plate cathode and an Mg rod anode in CH(3)CN to afford the corresponding phenylacetic acids in good yields. (C) 2010 Elsevier Ltd. All rights reserved.
• Electrochemical carboxylation of alpha-chloroethylbenzene in ionic liquids compressed with carbon dioxide

  Yusuke Hiejima, Masahiro Hayashi, Akihiro Uda, Seiko Oya, Hiroyuki Kondo, Hisanori Senboku, Kenji Takahashi

  PHYSICAL CHEMISTRY CHEMICAL PHYSICS 12 8 1953 - 1957 2010年 [査読有り][通常論文]
   

  Electrochemical carboxylation is conducted in ionic liquids compressed with carbon dioxide. It is found that the current efficiency increases with temperature and pressure. The diffusion coefficient of the substrate, which is obtained from the electrochemical measurements, also remarkably increases with temperature and pressure. The increase of the current efficiency is mainly explained by improvement in the mass transfer, and the promotion of the electrochemical carboxylation in the ionic liquid is achieved by pressurizing the carbon dioxide moderately.
• Synthesis of 2-aryl-3,3,3-trifluoropropanoic acids using electrochemical carboxylation of (1-bromo-2,2,2-trifluoroethyl)arenes and its application to the synthesis of beta,beta,beta-trifluorinated non-steroidal anti-inflammatory drugs

  Yusuke Yamauchi, Shoji Hara, Hisanori Senboku

  TETRAHEDRON 66 2 473 - 479 2010年01月 [査読有り][通常論文]
   

  Electrochemical carboxylation of (1-bromo-2,2,2-trifluoroethyl)arenes resulted in an efficient fixation of carbon dioxide to give the corresponding 2-aryl-3,3,3-trifluoropropanoic acids in good yields, and the present reactions were successfully applied to the synthesis of beta,beta,beta-trifluorinated non-steroidal anti-inflammatory drugs (NSAIDs). (C) 2009 Elsevier Ltd. All rights reserved.
• Hg cathode-free electrochemical detosylation of N,N-disubstituted p-toluenesulfonamides: mild, efficient, and selective removal of N-tosyl group

  Hisanori Senboku, Kazuo Nakahara, Tsuyoshi Fukuhara, Shoji Hara

  TETRAHEDRON LETTERS 51 2 435 - 438 2010年01月 [査読有り][通常論文]
   

  Hg cathode-free electrochemical detosylation of N,N-disubstituted p-toluenesulfonamides was successfully carried out by a constant Current electrolysis using an undivided cell equipped with a platinum cathode and a magnesium anode in the presence of an arene mediator. The deprotection proceeded efficiently and selectively under neutral and mild conditions with a stoichiometric amount of electricity without the use of an Hg cathode to obtain the corresponding secondary amines in good to excellent yields. (C) 2009 Elsevier Ltd. All rights reserved.
• Synthesis of 2-Aryl-2,3,3,3-tetrafluoropropanoic Acids, Tetrafluorinated Fenoprofen and Ketoprofen by Electrochemical Carboxylation of Pentafluoroethylarenes

  Yusuke Yamauchi, Kanae Sakai, Tsuyoshi Fukuhara, Shoji Hara, Hisanori Senboku

  SYNTHESIS-STUTTGART 20 3375 - 3377 2009年10月 [査読有り][通常論文]
   

  Synthesis of 2,3,3,3-tetrafluoro-2-(3-phenoxyphenyl)propanoic acid and 2-(3-benzoylphenyl)-2,3,3,3-tetrafluoropropanoic acid (tetrafluorinated fenoprofen and ketoprofen) was achieved by electrochemical carboxylation of pentafluoroethylarenes.
• Synthesis of Isoindolobenzazepine Alkaloids Based on Radical Reactions or Pd(0)-Catalyzed Reactions

  Yu Onozaki, Nobuhito Kurono, Hisanori Senboku, Masao Tokuda, Kazuhiko Orito

  JOURNAL OF ORGANIC CHEMISTRY 74 15 5486 - 5495 2009年08月 [査読有り][通常論文]
   

  Methods for synthesis of a ring system characteristic of isoindolobenzazepine alkaloids were studied. Synthesis of lennoxamine and a formal synthesis of chelenine were accomplished in a short route via radical or Pd(0)-catalyzed cyclization as the key step. An altenative approach based on a radical migration of a cyano group or Pd(0)-catalyzed carbonylation was also developed for both alkaloids.
• Synthesis of Isoindolobenzazepine Alkaloids Based on Radical Reactions or Pd(0)-Catalyzed Reactions. (vol 74, pg 5486, 2009)

  Yu Onozaki, Nobuhito Kurono, Hisanori Senboku, Masao Tokuda, Kazuhiko Orito

  JOURNAL OF ORGANIC CHEMISTRY 74 16 6414 - 6414 2009年08月 [査読無し][通常論文]
  
• Synthesis of Phenanthro[9,10-b]indolizidin-9-ones, Phenanthro[9,10-b]quinolizidin-9-one, and Related Benzolactams by Pd(OAc)(2)-Catalzed Direct Aromatic Carbonylation

  Satoshi Yamashita, Nobuhito Kurono, Hisanori Senboku, Masao Tokuda, Kazuhiko Orito

  EUROPEAN JOURNAL OF ORGANIC CHEMISTRY 2009 8 1173 - 1180 2009年03月 [査読有り][通常論文]
   

  Phenanthro[9,10-b]indolizidin-9-ones, phenanthro[9,10-b]-quinolizidin-9-one, and related benzolactam were synthesized by benzolactam ring formation using Pd(OAc)(2)-catalyzed direct aromatic carbonylation. This also constitutes a formal synthesis of the representative phenanthroindolizidine and -quinolizidine alkaloids (+/-)-tylophorine, (+/-)-antofine, and (+/-)-cryptopleurine. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
• An in situ high pressure FTIR study on molecular interactions of ketones, esters, and amides with dense phase carbon dioxide

  Y. Akiyama, S. Fujita, H. Senboku, C. M. Rayner, S. A. Brough, M. Arai

  JOURNAL OF SUPERCRITICAL FLUIDS 46 2 197 - 205 2008年09月 [査読有り][通常論文]
   

  The interactions between a variety of carbonyl compounds (ketones, esters, and amides) and dense phase CO2 have been investigated by in situ high pressure FTIR measurements. The gas and liquid phase spectra of these compounds have also been measured to provide accurate reference data, and these have been compared with those obtained in n-hexane and dense phase CO2 at a variety of pressures. The frequency of the carbonyl IR absorption is a measure of the strength of the carbonyl bond, and in the dense CO2 medium, is in between that observed in the gaseous and liquid phases. The substituent effect on the v(C=O) absorption bands is the same for the gas, liquid, and dense CO2 spectra and it is related to the electron donating nature of the substituents. When solutions of carbonyl compounds in n-hexane are diluted, the v(C=O) absorption bands are blue-shifted. In contrast, these bands in dense CO2 are red-shifted with increasing pressure (dilution by CO2). The red shift with increasing CO2 pressure is larger in amides > esters > ketones. (c) 2008 Elsevier B.V. All rights reserved.
• Rhodium-catalyzed ring-opening reactions of N-Boc-azabenzonorbornadiene with chiral amine nucleophiles derived from amino acids

  Yong-Hwan Cho, Nai-Wen Tseng, Hisanori Senboku, Mark Lautens

  SYNTHESIS-STUTTGART 15 2467 - 2475 2008年08月 [査読有り][通常論文]
   

  The rhodium-catalyzed ring-opening of azabenzonorbomadienes with chiral amino nucleophiles derived from amino acids such as (5)-proline and (R)-phenylglycine is reported. The desired products were obtained as a mixture of diastereomers, which Could be easily separated in high yield. Enantiomerically pure ring-fused nitrogen heterocycles and 1.2-diamines were also obtained by further transformation of the ring-opened products.
• Electrochemical carboxylation of alpha,alpha-difluorotoluene derivatives and its application to the synthesis of alpha-fluorinated nonsteroidal anti-inflammatory drugs

  Yusuke Yamauchi, Tsuyoshi Fukuhara, Shoji Hara, Hisanori Senboku

  SYNLETT 3 438 - 442 2008年02月 [査読有り][通常論文]
   

  Electrochemical carboxylation of alpha,alpha-difluorotoluene derivatives resulted in an efficient fixation of carbon dioxide to give the corresponding alpha-fluorophenylacetic acids in good yields, and this reaction was successfully applied to the synthesis of a-fluorinated nonsteroidal anti-inflammatory drugs (NSAIDs).
• An efficient synthesis of fluorocyclopentenes using fluoroalkylidenecarbenes

  Tong Guan, Kohei Takemura, Hisanori Senboku, Masanori Yoshida, Shoji Hara

  TETRAHEDRON LETTERS 49 1 76 - 79 2008年01月 [査読有り][通常論文]
   

  An efficient synthesis of fluorocyclopentenes is described. By treatment of (2-fluoroalkenyl)iodonium salts with potassium tert-butoxide, (alpha-fluoroalkylidene)carbenes were generated efficiently to give fluorocyclopentenes via 1,5-C-H insertion. Fluorocyclopentenes having a functionality, such as chlorine, acetoxy, or ketone, and a spiro fluorocyclopentene were synthesized in good yields. (C) 2007 Elsevier Ltd. All rights reserved.
• Polycyclic aromatic compounds-mediated electrochemical reduction of alkyl mesylates

  Hisanori Senboku, Megumi Takahashi, Tsuyoshi Fukuhara, Shoji Hara

  CHEMISTRY LETTERS 36 2 228 - 229 2007年02月 [査読有り][通常論文]
   

  Electrochemical reduction of alkyl mesylates was successfully carried out by using an undivided cell equipped with a Pt cathode and an Mg anode in the presence of biphenyl and t-BuOH. The reaction could proceed efficiently under mild conditions to give the corresponding alkanes in moderate to good yields. This procedure could also be applicable to chemoselective reduction of mesylates having functional groups such as epoxide, olefin, acetal, hydroxy, or cyano groups.
• Preparation of cyclic urethanes from amino alcohols and carbon dioxide using ionic liquid catalysts with alkali metal promoters

  Shin-ichiro Fujita, Hiroshi Kanamaru, Hisanori Senboku, Masahiko Arai

  INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES 7 10 438 - 450 2006年10月 [査読有り][通常論文]
   

  Several ionic liquids were applied as catalysts for the synthesis of cyclic urethanes from amino alcohols and pressurized CO2 in the presence of alkali metal compounds as promoters. A comparative study was made for the catalytic performance using different ionic liquids, substrates, promoters, and pressures. The optimum catalytic system was BMIM-Br promoted by K2CO3, which, for 1-amino-2-propanol, produced cyclic urethane in 40% yield with a smaller yield of substituted cyclic urea and no oligomeric byproducts. For other amino alcohols, cyclic urethanes, cyclic ureas, and/or undesired byproducts were produced in different yields depending on the substrates used. Possible reaction mechanisms are proposed.
• Electrochemical carboxylation of aliphatic ketones: Synthesis of beta-keto carboxylic acids

  Hisanori Senboku, Yusuke Yamauchi, Tsuyoshi Fukuhara, Shoji Hara

  ELECTROCHEMISTRY 74 8 612 - 614 2006年08月 [査読有り][通常論文]
   

  A constant current electrolysis of saturated aliphatic ketones in a CH3CN or DMF solution containing 0.1 mol din (-3) Bu4NBF4 with a platinum cathode and a magnesium anode under an atmospheric pressure of CO2 resulted in an efficient fixation of CO2 at a-position of carbonyl group in the ketones to give the corresponding P-keto carboxylic acids in moderate to good yields.
• Rhodium-catalyzed ring-opening reactions of N-boc-azabenzonorbornadienes with amine nucleophiles

  Yong-hwan Cho, Valentin Zunic, Hisanori Senboku, Madeline Olsen, Mark Lautens

  JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 128 21 6837 - 6846 2006年05月 [査読有り][通常論文]
   

  In the presence of a rhodium catalyst (5 mol %) generated in situ from [Rh(cod)Cl](2) and (S,S')- (R,R')-C-2-ferriphos(4a), the asymmetric ring-opening reaction of azabenzonorbornadienes (1a-m) with various aliphatic and aromatic amines (2a-I) proceeded with high enantioselectivity (up to > 99% ee) to give the corresponding 1,2-diamine derivatives 3 in high yields. In the specific case of pyrrolidine as nucleophile, Et3NHCI was necessary as an additive for good reactivity and enantioselectivity. Additionally, a practical protocol was developed for the ring-opening of 1a with volatile amines at elevated temperatures and standard pressure, using R2NH2I and i-Pr2NEt. The experimental results showed that the nature of the chiral ligand has the significant impact on the reactivity of the catalyst and the use of excess amount (2.2 eq to Rh) of the chiral ligand plays an important role to improve the enantioselectivity in the present asymmetric reaction.
• Stereoselective synthesis of (E)-beta-arylvinyl bromides by microwave-induced Hunsdiecker-type reaction

  CX Kuang, Q Yang, H Senboku, M Tokuda

  SYNTHESIS-STUTTGART 8 1319 - 1325 2005年05月 [査読有り][通常論文]
   

  (E)-beta-Arylvinyl bromides were readily prepared in a short reaction time (1-2 min) by microwave irradiation of the corresponding 3-arylpropenoic acids in the presence of N-bromosuccinimide and a catalytic amount of lithium acetate. Furthermore, two facile strategies for the efficient synthesis of (E)-beta-broMo-4-arylethynylstyrene and (E)-beta-bromo-4-arylstyrene have been developed by respectively combining Sonogashira and Suzuki coupling reaction with Hunsdiecker-type reaction. Formation of cis-alpha-bromo-beta-lactone by microwave irradiation of cis-cinnamic acid with NBS provides a useful support for the mechanistic study of the present halodecarboxylation reaction.
• Rapid debromination of vic-dibromoalkanes with zinc powder in acetic acid under microwave irradiation

  CX Kuang, Q Yang, H Senboku, M Tokuda

  JOURNAL OF CHEMICAL RESEARCH-S 5 282 - 284 2005年05月 [査読有り][通常論文]
   

  Microwave irradiation of vic-dibromoalkanes in acetic acid containing zinc powder for 1-2 min gave the corresponding alkenes in high yields.
• Synthesis of (Z)-1-bromo-1-alkenes and terminal alkynes from anti-2,3-dibromoalkanoic acids by microwave-induced reaction

  CX Kuang, Q Yang, H Senboku, M Tokuda

  TETRAHEDRON 61 16 4043 - 4052 2005年04月 [査読有り][通常論文]
   

  (Z)-1-Bromo-1-alkenes were stereoselectively prepared in high yields in a short reaction time by microwave irradiation of the corresponding anti-2,3-dibromoalkanoic acids in a Et3N/DMF system. A one-pot synthesis of terminal alkynes and enynes from 2,3-dibromoalkanoic acids were also developed by microwave-induced reaction. (c) 2005 Elsevier Ltd. All rights reserved.
• Stereospecific electrochemical carboxylation of beta-bromostyrene by use of nickel(II) catalyst

  CX Kuang, Q Yang, H Senboku, M Tokuda

  CHEMISTRY LETTERS 34 4 528 - 529 2005年04月 [査読有り][通常論文]
   

  Electrochemical carboxylation of (E)- and (Z)-beta-bromostyrenes (1) under an atmospheric pressure of carbon dioxide with a platinum cathode and a magnesium anode in the presence of 20 mol % of NiBr2 center dot bpy proceeded with retention of stereochemistry to give the corresponding (E)- or (Z)-cinnamic acids (2). The stereochemical outcome of nickel(II)-catalyzed electrochemical carboxylations was discussed by comparison with predominant formation of a (Z)-isomer from either (E)- or (Z)-beta-bromostyrenes.
• Stereoselective synthesis of (E)-beta-arylvinyl bromides by microwave-induced reaction of anti-3-aryl-2,3-dibromopropanoic acids using an AgOAc-AcOH system

  CX Kuang, H Senboku, M Tokuda

  TETRAHEDRON 61 3 637 - 642 2005年01月 [査読有り][通常論文]
   

  (E)-beta-Arylvinyl bromides were stereoselectively prepared in high yields by microwave irradiation of the corresponding anti-3-aryl-2,3-dibromopropanoic acids in AcOH in the presence of AgOAc for 0.5-3.0 min. (C) 2004 Elsevier Ltd. All rights reserved.
• A one-pot synthesis of terminal alkynes from anti-3-aryl-2,3-dibromopropanoic acids under microwave irradiation

  CX Kuang, H Senboku, M Tokuda

  CHEMISTRY LETTERS 34 1 28 - 29 2005年01月 [査読有り][通常論文]
   

  A facile one-pot synthesis of terminal alkynes was achieved by microwave irradiation of a mixture of anti-3-aryl-2,3-dibromopropanoic acids, Et3N and DMF and subsequent irradiation in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). This method requires short reaction time (1-2min) and gives terminal alkynes in high yields.
• Stereoselective synthesis of 5-7 membered cyclic ethers by deiodonative ring-enlargement using hypervalent iodine reagents

  T Abo, M Sawaguchi, H Senboku, S Hara

  MOLECULES 10 1 183 - 189 2005年01月 [査読有り][通常論文]
   

  Stereoselective synthesis of 5-7 membered cyclic ethers was achieved by deiodonative ring-enlargement of cyclic ethers having an iodoalkyl substituent. The reaction took place readily under mild conditions using hypervalent iodine compounds and an acetoxy or a trifluoroacetoxy group was introduced into the rings depending on the hypervalent iodine reagent employed. The use of hexafluoroisopropanol (HFIP) as solvent is critical.
• A convenient synthesis of highly substituted furans by microwave irradiation of ring-fused alkylidenecyclopropanes

  MA Chowdhury, H Senboku, M Tokuda

  SYNLETT 11 1933 - 1936 2004年09月 [査読有り][通常論文]
   

  Microwave irradiation of ring-fused alkylidenecyclopropanes under solvent-free conditions afforded highly substituted furans in good yields.
• Electrochemical carboxylation of bicyclo[n.1.0]alkylidene derivatives

  MA Chowdhury, H Senboku, M Tokuda

  TETRAHEDRON 60 2 475 - 481 2004年01月 [査読有り][通常論文]
   

  Electrochemical carboxylation of bicyclo[n.1.0]alkylidene derivatives (ring-fused alkylidenecyclopropanes) in a suitable aprotic solvent using a one-compartment electrochemical cell equipped with a platinum plate cathode and a zinc plate anode under an atmospheric pressure of carbon dioxide afforded either mono- or dicarboxylic acid in moderate to good yields. (C) 2003 Elsevier Ltd. All rights reserved.
• A new synthesis of ring-fused alkylidenecyclobutanes by ring-enlargement reaction of bicyclo[n.1.0]alkylidene derivatives

  MA Chowdhury, H Senboku, M Tokuda

  TETRAHEDRON LETTERS 44 16 3329 - 3332 2003年04月 [査読有り][通常論文]
   

  Bicyclo[n.1.0]alkylidene derivatives (ring-fused alkylidenecyclopropanes) reacted with diazomethane to give spiro-pyrazolines regioselectively. Thermal decomposition of spiro-pyrazolines resulted in ring-enlargement and afforded ring-fused alkylidenecyclobutanes (bicyclo[n.2.0]alkylidene derivatives) in high yields. (C) 2003 Elsevier Science Ltd. All rights reserved.
• Stereoselective synthesis of 2-methylenepyrrolizidines by tandem cyclization of N-propargylaminyl radicals

  H Hasegawa, H Senboku, Y Kajizuka, K Orito, M Tokuda

  TETRAHEDRON 59 6 827 - 832 2003年02月 [査読有り][通常論文]
   

  Tandem cyclization of N-propargylaminyl radicals, generated by N-chlorination of (E)-alk-4-enylamines 2a-d and 2f followed by treatment with tributyltin radical, afforded 2-methylenepyrrolizidines 3a-d and 3f in a highly stereoselective manner. A similar radical cyclization of (Z)-N-propargyl-1-methyl-5-phenylpent-4-enylamine (2e) gave pyrrolizidine 3b having the same stereochemistry as that obtained from the E isomer 2b. (C) 2003 Elsevier Science Ltd. All rights reserved.
• Selective hydrogenation of phenylacetylene with graphite intercalated platinum nanosheets

  M Shirai, BM Bhanage, H Senboku, S Fujita, M Arai

  JOURNAL OF THE JAPAN PETROLEUM INSTITUTE 45 6 420 - 421 2002年11月 [査読有り][通常論文]
   

  Platinum nanosheets between graphite layers were active for hydrogenation of ethynyl group of phenylacetylene but less active for that of aromatic rings of phenylacetylene and benzene due to its structural characteristics.
• Stereoselective preparation of 7-exo-amino-7-endo-substituted bicyclo[4.1.0]heptanes

  MA Chowdhury, H Senboku, M Tokuda, T Chiba

  TETRAHEDRON 58 9 1673 - 1677 2002年02月 [査読有り][通常論文]
   

  Bicyclo[4.1.0]heptan-7-one N,O-hemiacetals undergo substitution reaction with Wittig reagents (Ph3P==CHR3) to give stereoselectively the corresponding 7-exo-amino-7-endo-substituted bicyclo[4.1.0]heptanes in good yields. (C) 2002 Elsevier Science Ltd. All rights reserved.
• Facile and stereoselective synthesis of (E)-vinyl bromides by microwave-induced reaction of 1,1-dibromoalkenes using a diethyl phosphonate/EtONa/EtOH system

  CX Kuang, H Senboku, M Tokuda

  TETRAHEDRON 58 8 1491 - 1496 2002年02月 [査読有り][通常論文]
   

  (E)-Vinyl bromides were readily prepared from 1,1-dibromoalkenes by microwave irradiation within 1 min using a diethyl phosphonate/EtONa/EtOH system. This method utilizes cheap and environmentally friendly reagents, requires only a short reaction time, and gives (E)-vinyl bromides in high stereoselectivities and high yields. (C) 2002 Elsevier Science Ltd. All rights reserved.
• Convenient synthesis of cyclic alpha-alkoxyl-alpha,beta-unsaturated carboxylic acids by nickel-catalyzed electrochemical carboxylation of lactone enol triflates

  H Senboku, H Kanaya, M Tokuda

  SYNLETT 1 140 - 142 2002年01月 [査読有り][通常論文]
   

  Electrochemical carboxylation of lactone enol triflates in DMF containing a catalytic amount of NiBr2.bpy with a platinum cathode and a magnesium anode under an atmospheric pressure of CO2 gave the corresponding cyclic alpha-alkoxyl-alpha,beta-unsaturated carboxylic acids, captodative cycloalkenes, in good yields.
• A facile synthesis of ring-fused alkylidenecyclopropanes by olefination reaction of bicyclo[n.1.0]alkanone N,O-hemiacetals with Wittig reagents

  MA Chowdhury, H Senboku, M Tokuda, Y Masuda, T Chiba

  TETRAHEDRON LETTERS 42 40 7075 - 7078 2001年10月 [査読有り][通常論文]
   

  Ring-fused alkylidenecyclopropanes. bicyclo[n.1.0]alkylidene derivatives, were readily synthesized by olefination reaction of bicyclo[n.l.0]alkanone N,O-hemiacetals with Wittig reagents in good yields. (C) 2001 Elsevier Science Ltd. All rights reserved.
• Stereochemical study on electrochemical carboxylation of vinyl triflates

  H Senboku, H Kanaya, Y Fujimura, M Tokuda

  JOURNAL OF ELECTROANALYTICAL CHEMISTRY 507 1-2 82 - 88 2001年07月 [査読有り][通常論文]
   

  A stereochemical study on electrochemical carboxylation of ethoxycarbonyl- or phenyl-substituted vinyl triflates was carried out. Vinyl triflates in DMF with a platinum cathode and a magnesium anode underwent electrochemical carboxylation with retention of their geometries to give the corresponding alpha,beta -unsaturated carboxylic acids in moderate to good yields. The stereochemical outcome of these electrochemical carboxylations is discussed by comparison with predominant formation of a (Z)-isomer from either (E)- or (Z)-vinyl bromides. (C) 2001 Elsevier Science B.V. All rights reserved.
• Convenient and stereoselective synthesis of (Z)-1-bromo-1-alkenes by microwave-induced reaction

  CX Kuang, H Senboku, M Tokuda

  TETRAHEDRON LETTERS 42 23 3893 - 3896 2001年06月 [査読有り][通常論文]
   

  (Z)-l-Bromo-l-alkenes were stereoselectively prepared in high yields in a short reaction time (0.2 1.0 min) by microwave irradiation of the corresponding 2,3-dibromoalkanoic acids in DMF in the presence of triethylamine. (C) 2001 Elsevier Science Ltd. All rights reserved.
• Efficient electrochemical dicarboxylation of phenyl-substituted alkenes: Synthesis of 1-phenylalkane-1,2-dicarboxylic acids

  H Senboku, H Komatsu, Y Fujimura, M Tokuda

  SYNLETT 3 418 - 420 2001年03月 [査読有り][通常論文]
   

  Electrochemical dicarboxylation of phenyl-substituted alkenes in the presence of atmospheric pressure of carbon dioxide with a platinum plate cathode and a magnesium rod anode readily took place efficiently in a DMF solution containing 0.1 M Et4ClO4 to give the corresponding 1,2-dicarboxylic acids in high yields.
• Stereoselective synthesis of (E)-beta-arylvinyl halides by microwave-induced Hunsdiecker reaction

  CX Kuang, H Senboku, M Tokuda

  SYNLETT 10 1439 - 1442 2000年10月 [査読有り][通常論文]
   

  (E)-beta-Arylvinyl halides were prepared in high yields in a short reaction (1-2 min) by microwave irradiation of the corresponding 3-arylpropenoic acids in the presence of N-halosuccinimide and catalytic LiOAc.
• Exclusive 1,4-aryl migration in a stereoselective cyclization of N-benzylalk-4-enylaminyl radicals

  H Senboku, H Hasegawa, K Orito, M Tokuda

  TETRAHEDRON LETTERS 41 30 5699 - 5703 2000年07月 [査読有り][通常論文]
   

  Tandem cyclization of N-benzylalk-4-enylaminyl radicals readily occurs to give 1,4-aryl migration pyrrolidines, trans-N-methyl-2-alkyl-5-(1-phenylalkyl)pyrrolidines, exclusively. (C) 2000 Elsevier Science Ltd. All rights reserved.
• Divergent electrochemical carboxylation of vinyl triflates: new electrochemical synthesis of phenyl-substituted alpha,beta-unsaturated carboxylic acids and aliphatic beta-keto carboxylic acids

  H Senboku, Y Fujimura, H Kamekawa, M Tokuda

  ELECTROCHIMICA ACTA 45 18 2995 - 3003 2000年 [査読有り][通常論文]
   

  Electrochemical carboxylation of vinyl triflates using a magnesium anode, as a reactive metal electrode, was investigated. Alkyl-substituted vinyl triflates were electrolyzed in the presence of an atmospheric pressure of carbon dioxide to give beta-keto carboxylic acids as a sole products. On the other hand, electrochemical carboxylation of phenyl-substituted vinyl triflates gave alpha,beta-unsaturated carboxylic acids exclusively. These divergent electrochemical carboxylation resulted from chemoselective cleavage of O-S or C-O bond of vinyl triflate, which was affected by the presence or absence of phenyl substituents in the structure of starting vinyl triflates. (C) 2000 Elsevier Science Ltd. All rights reserved.
• Tandem cyclization of N-allylaminyl radicals: Stereoselective synthesis of 1,2,5-trisubstituted pyrrolizidines

  H Senboku, Y Kajizuka, H Hasegawa, H Fujita, H Suginome, K Orito, M Tokuda

  TETRAHEDRON 55 21 6465 - 6474 1999年05月 [査読有り][通常論文]
   

  Radical reaction of N-allylalk-4-enylaminyl radicals, generated from the corresponding N-chloroamines by treatment with Bu3SnH-AIBN in refluxing toluene, was carried out. Tandem cyclization of the resulting neutral aminyl radicals readily took place stereoselectively to give 1,2,5-trisubstituted pyrrolizidines and a pyrroloindole derivative as a sole product in good yields. The cyclization products contained only two stereoisomers in each reaction, indicating that both of the consecutive cyclizations proceeded in a stereoselective manner. (C) 1999 Elsevier Science Ltd. All rights reserved.
• New stereoselective synthesis of (+/-)-trans-2-butyl-5-heptyl-1-methylpyrrolidine, ant venom alkaloid, by aminyl radical cyclization

  H Senboku, H Hasegawa, K Orito, M Tokuda

  HETEROCYCLES 50 1 333 - 340 1999年01月 [査読有り][通常論文]
   

  New synthesis of (+/-)-trans-2-butyl-5-heptyl-1-methylpyrrolidine (1), ant venom alkaloid, was achieved by the use of stereoselective cyclization of aminyl radicals. Thus, orthoester Claisen rearrangement of 1-hexen-3-ol (2) gave (E)-ethyl 4-octenoate (3). Reaction of ester (3) with 2-methylaminopyridine and AlCl3 afford ed the corresponding N-methyl-N-(2-pyridyl)amide (4), which was treated with heptylmagnesium iodide at -78 degrees C to give (E)-4-pentadecen-8-one (5). Reductive amination of ketone (5) with methylamine gave N-methyl-1-heptyl-4-octenylamine (6). Treatment of amine (6) with NCS in toluene gave the corresponding N-chloroamine (12), and successive heating under reflux with Bu3SnH and AIBN resulted in stereoselective cyclization of the aminyl radical to give (+/-)-trans-2-butyl-5-heptyl-1-methylpyrrolidine (1) in a 59% yield. Similarly, 1-nonen-3-ol (7) was converted into N-methyl-1-butyl-4-undecenylamine (11), which was subjected to the aminyl radical cyclization to give 1 in a 49% yield.
• New electrochemical carboxylation of vinyl triflates. Synthesis of beta-keto carboxylic acids

  H Kamekawa, H Senboku, M Tokuda

  TETRAHEDRON LETTERS 39 12 1591 - 1594 1998年03月 [査読有り][通常論文]
   

  Electrochemical reduction of alicyclic vinyl triflates (1a-1e) in a DMF solution containing 0.1 M Bu4NBF4 under an atmospheric pressure of carbon dioxide with a platinum cathode and a magnesium anode resulted in the cleavage of an oxygen-sulfur bond of 1 to give the corresponding beta-keto carboxylic acids (2a-2e) in yields of 28-77%. (C) 1998 Elsevier Science Ltd. All rights reserved.
• Synthesis of (+/-)-nitramine and (+/-)-isonitramine by utilizing stereoselective reduction of ethyl 1-(3-bromopropyl)-2-oxocyclohexanecarboxylate

  H Senboku, M Hatazawa, K Orito, M Tokuda

  HETEROCYCLES 46 413 - 420 1997年12月 [査読有り][通常論文]
   

  Formal synthesis of (+/-)-nitramine (1) and (+/-)-isonitramine (2) was achieved. Thus, the reduction of ethyl 1-(3-bromopropyl)-2-oxocyclohexanecarboxylate (6) with NaBH4 in MeOH gave the corresponding cyclohexanol (7) having cis geometry between hydroxyl and ester groups, predominantly. On the other hand, the trans located isomer (8) was preferentially obtained by reduction with LiAl(OBu')(3)H in THF. Treatment of the former reduction product (7) having cis geometry with benzylamine at 60 degrees C gave cis located ethyl 1-(3-(N-benzylamino)-propyl)-2-hydroxycyclohexanecarboxylate (9), which was further treated with BuLi to give a spirolactam, 2-benzyl-7-hydroxy-2-azaspiro[5,5]undecan-1-one (11) in 84% yield. Reduction of the lactam (11) with BH3 . SMe2 in THF gave N-benzylnitramine (13). In a similar manner, N-benzylisonitramine (14) was synthesized from trans located hydroxyaminoester (10).
• New and convenient synthesis of 3-methylenepent-4-enoic acid by electrochemical carboxylation

  M Tokuda, A Yoshikawa, H Suginome, H Senboku

  SYNTHESIS-STUTTGART 10 1143 - & 1997年10月 [査読有り][通常論文]
   

  Electrochemical carboxylation of 2-bromomethyl-1,4-dibromobut-2-ene (1) with atmospheric carbon dioxide in a DMF solution containing Bu4NI with a platinum cathode and a manganin or nickel anode gave 3-methylenepent-4-enoic acid (3) in 57 % yield. The acid 3 can be used as a diene in an aqueous intermolecular Diels-Alder reaction with dimethyl fumarate to give the adduct 7 in 67 % yield.
• Synthesis of alpha,beta-unsaturated carboxylic acids by nickel(II)-catalyzed electrochemical carboxylation of vinyl bromides

  H Kamekawa, H Kudoh, H Senboku, M Tokuda

  CHEMISTRY LETTERS 9 917 - 918 1997年 [査読有り][通常論文]
   

  Electrochemical carboxylation of alkyl-substituted vinyl bromides (1a-1g) in the presence of 20 mol% of NiBr2.bpy under an atmospheric pressure of carbon dioxide with a platinum cathode and a magnesium anode gave the corresponding alpha,beta-unsaturated carboxylic acids (2a-2g) in yields of 53-82%.
• Photoinduced molecular transformations .160. Furan annelation of 2-hydroxynaphthoquinone involving photochemical addition and radical fragmentation: Exclusion of the intermediacy of [2+2] cycloadduct in a one-pot formation of furanoquinones by the regioselective 3+2 photoaddition of hydroxyquinones with alkenes

  H Senboku, Y Kajizuka, K Kobayashi, M Tokuda, H Suginome

  HETEROCYCLES 44 341 - 348 1997年01月 [査読有り][通常論文]
   

  2-Acetoxy-1,4-naphthoquinone underwent [2+2] photoaddition to 2-methylpropene, giving a cyclobutanol acetate exclusively. Hydrolysis of the acetate with acid gave the corresponding cyclobutanol, which was stable under the conditions of an alkene-quinone photoaddition; hydrolysis with a base gave a fused 1-indanone derivative. Photolysis of the hypoiodite generated from the cyclobutanol derivative with mercury(II) oxide-iodine in benzene induced a beta-scission of the cyclobutanoxyl radical to give a 2,3-dihydronaphtho[2,3-b]furan-4,9-dione and its [1,2-b]furan-4,5-dione isomer.
• Facile synthesis of aryl-substituted 2-alkenoic acids by electroreductive carboxylation of vinylic bromides using a magnesium anode

  H Kamekawa, H Senboku, M Tokuda

  ELECTROCHIMICA ACTA 42 13-14 2117 - 2123 1997年 [査読有り][通常論文]
   

  Electrochemical carboxylation of phenyl-substituted vinylic bromides in the presence of atmospheric carbon dioxide using a platinum cathode and a magnesium anode gave the corresponding alpha,beta-unsaturated carboxylic acids in 63-92% isolated yields. A precursor of ibuprofen, 2-(pisobutylphenyl)propenoic acid, was readily obtained in a 93% yield by a similar electrochemical carboxylation of 1-bromo-1-(p-isobutylphenyl)ethene. Stereochemical studies showed that thermodynamically less stable Z-isomers were preferentially produced from either E- or Z-vinylic bromides in these electrochemical carboxylations. (C) 1997 Elsevier Science Ltd.
• Photoinduced molecular transformations .159. Formation of some furonaphthyridinones by selective beta-scission of cyclobutanoxyl radicals generated from [2+2] photoadducts of 4-hydroxy-1-phenyl [1,8] naphthyridin-2(1H)-one with alkenes

  H Senboku, M Takashima, M Suzuki, K Kobayashi, H Suginome

  TETRAHEDRON 52 17 6125 - 6138 1996年04月 [査読有り][通常論文]
   

  The [2+2] photoaddition of 4-hydroxy-1-phenyl[1,8]naphthyridin-2(1H)-one 7 with various alkenes in methanol gave regioselectively the corresponding head-to-tail adducts (8,9, and 11). The photolysis of the hypoiodites generated by the in situ reaction of the cyclobutanol adducts 8,9, and 11 with excess mercury(II) oxide-iodine reagent in benzene induced a regioselective scission of their non-ring junction bond of the corresponding alkoxyl radicals to give substituted 3,9-dihydro-9-phenylfuro[2,3-b][1,8]naphthyridin-4(2H)-one (12 and 15) and/or substituted 3,5-dihydro-5-phenylfuro[3,2-c][1,8]naphthyridin-4-(2H)-one (13,14, and 16). An unusual byproduct 12a was formed in the photolysis of the hypoiodite of the [2+2] photoadduct 8a of 4-hydroxy-1-phenyl[1,8]naphthyridin-2-(1H)-one with isobutene. (C) 1996 Elsevier Science Ltd.
• PHOTOINDUCED MOLECULAR-TRANSFORMATIONS .156. NEW PHOTOADDITIONS OF 2-HYDROXY-1,4-NAPHTHOQUINONES WITH NAPHTHOLS AND THEIR DERIVATIVES

  H SUGINOME, A KONISHI, H SAKURAI, H MINAKAWA, T TAKEDA, H SENBOKU, M TOKUDA, K KOBAYASHI

  TETRAHEDRON 51 5 1377 - 1386 1995年01月 [査読有り][通常論文]
   

  Dinaphtho[2,1-b;1',2'-d]furan-12,13-diones are produced in one-step in up to 45% yield by a (3+2) photoaddition of 2 hydroxy-1,4-naphthoquinones with 2-naphthol, while (+/-)-(6a alpha,6b beta,12a beta,12b alpha)-6a,6b,12a,12b-tetrahydro-12b-hydroxydinaphtho-[1,2-a;1',2'-c]cyclobutenes (14-16%), arising from the stereoselective addition of a (2+2) photoaddition, are products in the photoaddition of 2-hydroxy-1,4-naphthoquinone with 2-methoxynaphthalene and with 2-naphthyl acetate. The photoaddition of 2-hydroxy-1,4-naphthoquinone with 2-methoxynaphthalene also gave 2-hydroxy-3-(2-methoxynaphth-1-yl)-1,4-naphthoquinone (23%) as an accompanying product. Similar irradiation of a solution of 2-hydroxy-1,4-naphthoquinone with 1-methoxynaphthalene in acetone gave cis-6a,13a-dihydro-13a-methoxydinaphtho[1,2-b;2',3'-d]furan-7,12-dione arising from a (3+2) photoaddition in 24% yield. The probable mechanisms for the formation of the photoadducts are discussed.
• PHOTOINDUCED MOLECULAR-TRANSFORMATIONS .154. ON THE MECHANISM OF THE FORMATION OF THE 5-IODOPENTYL FORMATE IN THE PHOTOLYSIS OF CYCLOPENTANOL HYPOIODITE IN SOLUTION IN THE PRESENCE OF MERCURY(II) OXIDE-IODINE

  H SUGINOME, H SENBOKU

  TETRAHEDRON 50 46 13101 - 13112 1994年11月 [査読有り][通常論文]
   

  O-18-labelling experiments established that the formation of 5-iodopentyl formate in the photolysis of cyclopentanol hypoiodite in the presence of excess mercury(II) oxide-iodine in benzene involves the following pathway: a) a p-scission of a cyclopentyloxy radical to rearrange to a primary 5-oxopentyl radical, which generates the corresponding carbocation by a metal ion-assisted one-electron oxidation; b) an intramolecular addition of the 5-oxopentyl cation to the formyl oxygen to generate a tetrahydropyranyl cation; c) a combination of the tetrahydropyranyl cation with diiodine oxide (I2O) to form a lactol hypoiodite; d) generation of a carbon-centred radical by a selective beta-scission of a carbon-carbon bond of an alkoxyl radical generated from the lactol hypoiodite; e) abstraction of an iodine by the carbon-centred radical from an iodine molecule to form the 5-iodopentyl formate. 5-Iodopentyl formate is also produced by prolonged irradiation of a solution of 5-iodopentanal in the presence of mercury(II) oxide and iodine in benzene with Pyrex-filtered light. The formate in this case should be formed through the generation of the 5-oxopentyl cation (mentioned above) by mercury-assisted ionization of its carbon-iodine bond, followed by the same pathway as that mentioned above.
• PHOTOINDUCED MOLECULAR-TRANSFORMATIONS .149. STEREOSPECIFIC PHOTOADDITIONS AND PHOTOREARRANGEMENTS OF THE OXIMES OF SOME STEROIDAL ALPHA,BETA-UNSATURATED CYCLIC-KETONES AND THEIR DEUTERIO DERIVATIVES

  H SUGINOME, K OHSHIMA, Y OHUE, T OHKI, H SENBOKU

  JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1 21 3239 - 3250 1994年11月 [査読有り][通常論文]
   

  The photolysis of several steroidal cyclic alpha,beta-unsaturated ketone oximes as model substrates in methanol showed that these excited oximes react in either one of two ways, depending upon their structural features. Thus, while the excited oximes. such as those of 5 alpha-Cholest-4-en-6-one and the 5-en-4-one oxime, having their C=C bond at their ring junction, lead to the corresponding enamides (15-40%) arising from a photorearrangement, the excited oximes, having their C=C bond at their non-ring junction (such as the oximes of 5 alpha-cholest-2-en-1-one and the 3-en-2-one). principally lead to photoisomerization to form transient trans geometrical isomers from which stereospecific additions of proton or methanol to their trans C=C bond take place. The irradiation of (E)-5 alpha-cholest-2-en-1-one oxime in benzene-acetic acid (94:6) gave 1-aza-4a-homo-5a-cholest-3-en-2-one arising from a regioselective photorearrangement, while irradiation of the oxime in methanol gave 3 beta-methoxy-S alpha-cholestan-1-one arising from photoaddition in low yield. Thus, organic acid accelerates the photorearrangement to the lactam in competition to the alpha-fission. In contrast to these photochemical transformations, ground-state Beckmann rearrangements of (E)-cholest-4-en-6-one oxime and (E)-cholest-5-en-4-one oxime. having their C=C bond at their ring junction, under the standard conditions gave the corresponding cyclic enamines. Treatment of (E)-5 alpha-cholest-2-en-1-one oxime under the standard conditions of the Beckmann rearrangement. however, gave an unsaturated nitrile as well as the corresponding enamide. The regioselectivities of the formation of cyclic enamine and enamides in the photo- and nonphoto-rearrangements, as well as the structure-photoproduct correlation of the oximes, are discussed.
• PHOTOINDUCED MOLECULAR-TRANSFORMATIONS .145. REGIOSELECTIVE [3+2]-PHOTOADDITIONS OF 2-HYDROXYPHENANTHRENE-1,4-DIONE WITH ELECTRON-RICH ALKENES AND PHENYLACETYLENE - NEW ONE-STEP SYNTHESIS OF 9,10-DIHYDROPHENANTHRO-[2,3-B]FURAN-7,11-DIONES AND 2-PHENYLPHENANTHRO[2,3-B]FURAN-7,11-DIONE

  H SUGINOME, H KAMEKAWA, H SAKURAI, A KONISHI, H SENBOKU, K KOBAYASHI

  JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1 4 471 - 475 1994年02月 [査読有り][通常論文]
   

  The irradiation of 2-hydroxyphenanthrene-1,4-dione and various electron-rich alkenes such as ethyl vinyl ether, isobutene, 1-methoxycyclohexene and 3,4-dihydro-2H-pyran in acetone with Pyrex-filtered light gave 9,10-dihydrophenanthro[2,3-b]furan-7,11-diones arising from regioselective [3 + 2] photoaddition in 25-50% yields. A [3 t 2] photoadduct, 9-phenylphenanthro [2,3-b]furan-7,11-dione, can be similarly formed in low yield when 2-hydroxyphenanthrene-1,4-dione and phenylacetylene in acetone are irradiated with Pyrex-filtered light. In contrast, the irradiation of 2-hydroxyphenanthrene-1,4-dione and alkenes such as methyl acrylate, acrytonitrile, cyclohexene. isopropenyl acetate. propenyl acetate, vinyl acetate, 1-phenylprop-1-yne or trimethylsilylacetylene in acetone gave only a dimer in 42-52% yields, no [3 + 2] photoadducts being formed.
• PHOTOINDUCED MOLECULAR-TRANSFORMATIONS .147. [2+2] PHOTOADDITION OF PROTECTED 4-HYDROXY-1(2H)-ISOQUINOLINONE WITH AN ELECTRON-DEFICIENT ALKENE AND THE FORMATION OF A 3,6-EPOXY-3,4,5,6-TETRAHYDRO-2-BENZAZOCIN-1(2H)-ONE VIA A BETA-SCISSION OF CYCLOBUTANOXYL RADICALS GENERATED FROM THE RESULTING PHOTOADDUCT

  H SUGINOME, Y KAJIZUKA, M SUZUKI, H SENBOKU, K KOBAYASHI

  HETEROCYCLES 37 1 283 - 288 1994年01月 [査読有り][通常論文]
   

  The direct irradiation of 4-benzyloxycarbonyloxy-2-methyl-1(2H)-isoquinolinone gave a 1 to 1 ratio of two stereoisomers of [2+2] photoadducts in 97% yield. Removal of the protecting group from the adducts by hydrogenolysis gave the corresponding cyclobutanols, (1 alpha, 2a alpha, 8b alpha)-(+/-)-1-cyano-1,2a,3,8b-tetrahydro-8 b-hydroxy-3 -methylcyclobut[c]-isoquinolin-4(2H)-one and its (1 alpha, 2a beta, 8b beta)- isomer in 78 and 67% yields. The photolysis of the hypoiodite generated in situ from the (1 alpha, 2a alpha, 8b alpha)-(+/-)-cyclobutanol with mercury(II) oxide - iodine in benzene induced a regioselective beta-scission at the ring fusion bond of the cyclobutanoxyl radical to give 5-cyano-3,6-epoxy-3,4,5,6-tetrahydro-6-hydroxy-2-methyl-2- benzazocin-1(2H)-one in 76% yield. The cyano substituent and the amide nitrogen play a decisive role in directing the bond to be cleaved.
• Photoinduced molecular transformations. Part 145. Regioselective [3 + 2] photoadditions of 2-hydroxyphenanthrene-1,4-dione with electron-rich alkenes and phenylacetylene: New one-step synthesis of 9,10-dihydrophenanthro[2,3-b]furan-7,11-diones and 2-phenylphenanthro[2,3-b]furan-7,11-dione

  Hiroshi Suginome, Hisato Kamekawa, Hideo Sakurai, Atsushi Konishi, Hisanori Senboku, Kazuhiro Kobayashi

  Journal of the Chemical Society, Perkin Transactions 1 471 - 475 1994年 [査読有り][通常論文]
   

  The irradiation of 2-hydroxyphenanthrene-1, 4-dione and various electron-rich alkenes such as ethyl vinyl ether, isobutene, 1-methoxycyclohexene and 3,4-dihydro-2H-pyran in acetone with Pyrexfiltered light gave 9,10-dihydrophenanthro[2,3-b]furan-7,11-diones arising from regioselective [3 + 2] photoaddition in 25-50% yields. A [3 + 2] photoadduct, 9-phenylphenanthro[2,3-b]furan-7,11-dione, can be similarly formed in low yield when 2-hydroxyphenanthrene-1,4-dione and phenylacetylene in acetone are irradiated with Pyrex-filtered light. In contrast, the irradiation of 2-hydroxyphenanthrene-1,4-dione and alkenes such as methyl acrylate, acrylonitrile, cyclohexene, isopropenyl acetate, propenyl acetate, vinyl acetate, 1-phenylprop-1-yne or trimethylsilylacetylene in acetone gave only a dimer in 42-52% yields, no [3 + 2] photoadducts being formed. © 1994 by the Royal Society of Chemistry. All Rights Reserved.
• PHOTOINDUCED MOLECULAR-TRANSFORMATIONS .134. PHOTOINDUCED STEREOSPECIFIC ADDITION OF METHANOL TO 5-BETA-CHOLEST-1-EN-3-ONE OXIME AND PHOTOINDUCED DECONJUGATION OF ITS 1-METHYL DERIVATIVE INVOLVING STEREOSPECIFIC PROTON-TRANSFER

  H SUGINOME, A NAGAOKA, H SENBOKU

  JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1 22 3103 - 3110 1992年11月 [査読有り][通常論文]
   

  Irradiation of 5beta-cholest-1-en-3-one oxime 14 in methanol gave 1alpha-methoxy-5beta-cholestan-3-one oxime 16, arising from the photoaddition of methanol to the double bond of the enone oxime. 1alpha-Methoxy-5beta-cholestan-3-one 17 as well as 10beta-methoxy-5(10 --> 1)abeo-1beta(H), 5beta, 10alpha(Me)cholestan-3-one 15, arising from a skeletal rearrangement of 5beta-cholest-1-en-3-one (generated from the oxime), were the accompanying products in this photoreaction. Deuterium-labelling studies confirmed that the formation of 1alpha-methoxy-5beta-cholestan-3-oxime 16 involves a stereospecific syn addition of methanol to the photogenerated, twisted, ground-state double bond of the oximes B from the rear side of the steroidal framework. Irradiation of 1-methyl-5beta-cholest-1-en-3-one oxime 23 in methanol, on the other hand, gave almost exclusively 1-methylene-5beta-cholestan-3-one oxime 24, arising from photodeconjugation of the alpha,beta-double bond to the beta,gamma-position. A deuterium-labelling study established that deuterium is stereospecifically introduced at the 2beta-position of 1-methyl-5beta-cholest-1-en-3-one oxime 23 in the photodeconjugation in methanol [H-2]ol while deuterium is stereospecifically introduced at the 2alpha-position in the photodeconjugation of its 5alpha-isomer 6. These results are fully consistent with our previously proposed pathway concerning the photodeconjugation of 1-methyl-5alpha-cholest-1-en-3-one oxime 6; the stereospecific addition of a proton to the photogenerated, twisted double bond of the oxime D from the rear side of the steroidal framework was followed by the loss of a proton from the 1-methyl group of the resulting carbocation intermediate. Neither the isoxazole derivative, a product in the photoreaction of 5alpha-cholest-1-en-3-one oxime 1, nor the unsaturated lactam from a photo-Beckmann rearrangement was formed in the photoreactions of either 5beta-cholest-1-en-3-one oxime 14 or its 1-methyl derivative 23.
• EFFICIENT FORMATION OF A SPIROTETRAHYDROFURAN RING BY THE IONIC CYCLIZATION OF BISHOMOALLYL TERTIARY ALCOHOLS VIA THEIR HYPOIODITES

  H SUGINOME, H SENBOKU, A TSUNETOSHI

  JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1 21 2917 - 2923 1992年11月 [査読有り][通常論文]
   

  Spirotetrahydrofuran derivatives are produced in high yields by an intramolecular cyclization of several steroidal bishomoallyl tertiary alcohols in benzene containing mercury(II) oxide and iodine at room temperature in the dark. 2-Hydroxy-2-(but-3-enyl)tetrahydrofuran thus cyclizes to give a mixture of the corresponding diastereoisomeric spirotetrahydrofurans in the dark. An ionic mechanism for the formation of the tetrahydrofuran ring, which involves the formation of the hypoiodite followed by the cyclization of its iodonium ion, is proposed based on studies concerning several model substrates.
• PHOTOINDUCED MOLECULAR-TRANSFORMATIONS .133. NEW PHOTOINDUCED DECONJUGATION OF STEROIDAL ALPHA,BETA-UNSATURATED CYCLIC KETONE OXIME INTO THE BETA,GAMMA-UNSATURATED ISOMER INVOLVING STEREOSPECIFIC PROTON-TRANSFER

  H SUGINOME, T OHKI, A NAGAOKA, H SENBOKU

  JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1 14 1849 - 1854 1992年07月 [査読有り][通常論文]
   

  Irradiation of 1-methyl-5-alpha-cholest-1-en-3-one oxime or its 4,4-dimethyl derivative in either a protic or an aprotic solvent gave 1-methylene-5-alpha-cholestan-3-one oxime or the corresponding 4,4-dimethyl derivative, arising from an unprecedented photodeconjugation of alpha,beta-enone oximes into the beta,gamma-isomers. Neither the expected isoxazole derivative (a product in the photoreaction of 5-alpha-cholest-1-en-3-one oxime or its 4,4-dimethyl derivative) nor the unsaturated lactam that arises from a photo-Beckmann rearrangement was formed. Deuterium-labelling studies on the photoreactions of 1-methyl-5-alpha-cholest-1-en-3-one oxime established that either a proton or a deuteron is stereospecifically introduced at the 2-alpha-position of the steroidal oxime in this photodeconjugation. A pathway which involves the sterospecific addition of either a proton or deuteron to the photogenerated, twisted double bond of the oximes from the rear side of the steroidal framework, followed by the loss of a proton or deuteron from the 1-methyl group of the resulting carbocation intermediate, is proposed regarding the formation of beta,gamma-unsaturated oximes from the excited alpha,beta-unsaturated oximes.
• Photoinduced molecular transformations. Part 131. Synthesis of 18-norsteroids, deoxofukujusonorone and the related steroids, based on a selective β-scission of alkoxyl radicals as the key step

  Hiroshi Suginome, Yutaka Nakayama, Hisanori Senboku

  Journal of the Chemical Society, Perkin Transactions 1 14 1837 - 1842 1992年 [査読有り][通常論文]
   

  A new transformation of steroids into 18-norsteroids under mild conditions is described. The key step was a regioselective β-scission of the alkoxyl radicals generated by photolysis of the hypoiodite of 18-hydroxy-18,20α-epoxy steroids, prepared by photolysis of steroidal 20α-ol nitrites followed by deoximation of the resulting 18-hydroxyimino-20α-hydroxy steroid with sodium nitrite and acetic acid. 3β-Hydroxypregn-5-en-20-one (pregnenolone) was thus transformed into 3β-hydroxy-18-norpregna-5,13-dien-20-one (12-deoxofukujusonorone) in 10 steps. © Royal Society of Chemistry.
• Photoinduced molecular transformations. Part 130. Novel stereospecific photorearrangement and stereospecific addition of methanol in steroidal α,β-unsaturated cyclic ketone oximes

  Hiroshi Suginome, Makoto Kaji, Toshiharu Ohtsuka, Shinji Yamada, Takashi Ohki, Hisanori Senboku, Akio Furusaki

  Journal of the Chemical Society, Perkin Transactions 1 4 427 - 432 1992年 [査読有り][通常論文]
   

  Irradiation of 5α-cholest-1-en-3-one oxime or its 4,4-dimethyl derivative in a protic or an aprotic solvent gave 4'α,5'-dihydro-4-nor-5α-cholest-1-eno[2,1-c]isoxazole or the corresponding 3,3-dimethyl derivative arising from an unprecedented photorearrangement. The molecular structure of the former was established by X-ray crystallographic analysis. 1β-Methoxy-5α-cholestan-3-one oximes or their 4,4-dimethyl derivatives, arising from an unprecedented photoaddition of methanol to the double bond of the enone oximes, were the accompanying products in both of these photoreactions and no lactams were formed. Deuterium-labelling studies on the photoreactions of 5α-cholest-1-en-3-one oxime and its trideuteriated derivative established that a deuteron or a proton is stereospecifically introduced at the 2α-position of the Steroidal oxime in this photorearrangement. A pathway which involves an unprecedented stereospecific addition of a proton or a deuteron to the photogenerated, twisted double bond of the oximes from the rear side, followed by fragmentation of the resulting carbocation and an intramolecular 1,3-dipolar addition of the nitrite oxide intermediate, is proposed regarding the formation of the isoxazole from the excited oximes. Deuterium-labelling studies also established that the addition of methanol to the double bond of the oximes is stereospecific too. On the basis of the labelling study it is concluded that the mechanism for the photoaddition of the methanol involves a stereospecific syn addition of the methanol to the photogenerated, twisted, ground-state double bond of the oximes from the rear side. © Royal Society of Chemistry.
• PHOTOINDUCED MOLECULAR-TRANSFORMATIONS .112. TRANSFORMATION OF STEROIDS INTO RING-A-AROMATIZED STEROIDS AND 19-NORSTEROIDS INVOLVING A REGIOSELECTIVE BETA-SCISSION OF ALKOXYL RADICALS - SYNTHESIS OF 2 MARINE NATURAL-PRODUCTS, 19-NOR-5-ALPHA-CHOLESTAN-3-BETA-OL AND 19-NORCHOLEST-4-EN-3-ONE, AND NEW SYNTHESIS OF ESTRONE AND 19-NORTESTOSTERONE

  H SUGINOME, H SENBOKU, S YAMADA

  JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1 8 2199 - 2205 1990年08月 [査読有り][通常論文]
  
• Photoinduced molecular transformations. Part 112. Transformation of steroids into ring-A-aromatized steroids and 19-norsteroids involving a regioselective β-scission of alkoxyl radicals; synthesis of two marine natural products, 19-nor-5α-cholestan-3β-ol and 19-norcholest-4-en-3- one, and new synthesis of estrone and 19-nortestosterone

  Hiroshi Suginome, Hisanori Senboku, Shinji Yamada

  Journal of the Chemical Society, Perkin Transactions 1 8 2199 - 2205 1990年 

  A new transformation of steroids into 19-norsteroids and ring-A-aromatized steroids is described. The transformation method involves the removal of the 10β-methyl group by a regioselective β-scission of alkoxyl radicals. Cholesterol was transformed into two marine natural products, 19-nor-5α-cholestan-3β-ol and 19-norcholest-4-en-3-one, and into 19-norcholesta-1,3,5(10)-trien-3-ol. Transformations of 3β-hydroxyandrost- 5-en-17-one into 19-nortestosterone, estrone, and the related estranes are also described.
• PHOTOINDUCED MOLECULAR TRANSFORMATIONS .93. A NEW AROMATIZATION OF RING-A OF STEROIDS - SYNTHESIS OF ESTRONE

  H SUGINOME, H SENBOKU, S YAMADA

  TETRAHEDRON LETTERS 29 1 79 - 80 1988年 [査読有り][通常論文]
  

書籍

• Encyclopedia of Applied Electrochemistry

  SENBOKU Hisanori (範囲:Electrochemical Fixation of Carbon Dioxide (Cathodic Reduction in the Presence of Carbon Dioxide))
  Springer Science+Business Media, New York 2014年
• Transformation and Utilization of Carbon Dioxide

  SENBOKU Hisanori (範囲:Electrochemical Fixation of Carbon Dioxide)
  Springer-Verlag, Berlin Heidelberg 2014年
• 超臨界二酸化炭素中での有機電解合成

  新しい溶媒を用いた有機合成、S&T出版 2013年 130-142
• 有機カルボン酸の高効率合成

  超臨界流体プロセスの実用化, 技術情報協会 2000年
• Synthesis of β-Keto Acid by Electrochemical Carboxylation of Vinyl Triflates

  Novel Trends in Electroorganic Synthesis, ed. by Torii S., Springer-Verlag, Tokyo 1998年
• Electrochemical Carboxylation of Several Organic Halides in Supercritical Carbon Dioxide

  Novel Trends in Electroorganic Synthesis, ed. by Torii S., Springer-Verlag, Tokyo 1998年
• New and Convenient Synthesis of 3-Methylene-4-pentenoic Acid by Electrochemical Carboxylation

  Novel Trends in Electroorganic Synthesis, ed. by Torii S., Springer-Verlag, Tokyo 1998年
• Synthesis of α,β-Unsaturated Carboxylic Acids by Electrochemical Carboxylation of Vinyl Bromides and Its application to the Synthesis of Anti-inflammatory Agents

  Novel Trends in Electroorganic Synthesis, ed. by Torii S., Springer-Verlag, Tokyo 1998年

その他活動・業績

• A convenient synthesis of highly substituted furans by microwave irradiation of ring-fused alkylidenecyclopropanes

  MA Chowdhury, H Senboku, M Tokuda SYNLETT 1933-1936 (11) 1933 -1936 2004年09月 [査読無し][通常論文]
   

  Microwave irradiation of ring-fused alkylidenecyclopropanes under solvent-free conditions afforded highly substituted furans in good yields.
• Electrochemical carboxylation of bicyclo[n.1.0]alkylidene derivatives

  MA Chowdhury, H Senboku, M Tokuda TETRAHEDRON 60 (2) 475 -481 2004年01月 [査読無し][通常論文]
   

  Electrochemical carboxylation of bicyclo[n.1.0]alkylidene derivatives (ring-fused alkylidenecyclopropanes) in a suitable aprotic solvent using a one-compartment electrochemical cell equipped with a platinum plate cathode and a zinc plate anode under an atmospheric pressure of carbon dioxide afforded either mono- or dicarboxylic acid in moderate to good yields. (C) 2003 Elsevier Ltd. All rights reserved.
• A new synthesis of ring-fused alkylidenecyclobutanes by ring-enlargement reaction of bicyclo[n.1.0]alkylidene derivatives

  MA Chowdhury, H Senboku, M Tokuda TETRAHEDRON LETTERS 44 (16) 3329 -3332 2003年04月 [査読無し][通常論文]
   

  Bicyclo[n.1.0]alkylidene derivatives (ring-fused alkylidenecyclopropanes) reacted with diazomethane to give spiro-pyrazolines regioselectively. Thermal decomposition of spiro-pyrazolines resulted in ring-enlargement and afforded ring-fused alkylidenecyclobutanes (bicyclo[n.2.0]alkylidene derivatives) in high yields. (C) 2003 Elsevier Science Ltd. All rights reserved.
• Stereoselective synthesis of 2-methylenepyrrolizidines by tandem cyclization of N-propargylaminyl radicals

  H Hasegawa, H Senboku, Y Kajizuka, K Orito, M Tokuda TETRAHEDRON 59 (6) 827 -832 2003年02月 [査読無し][通常論文]
   

  Tandem cyclization of N-propargylaminyl radicals, generated by N-chlorination of (E)-alk-4-enylamines 2a-d and 2f followed by treatment with tributyltin radical, afforded 2-methylenepyrrolizidines 3a-d and 3f in a highly stereoselective manner. A similar radical cyclization of (Z)-N-propargyl-1-methyl-5-phenylpent-4-enylamine (2e) gave pyrrolizidine 3b having the same stereochemistry as that obtained from the E isomer 2b. (C) 2003 Elsevier Science Ltd. All rights reserved.
• 超臨界二酸化炭素中における電気化学的手法による有機合成 (特集 超臨界二酸化炭素中における有機合成反応)

  仙北 久典, 徳田 昌生 ファインケミカル 31 (16) 50 -60 2002年09月15日
• Facile and stereoselective synthesis of (E)-vinyl bromides by microwave-induced reaction of 1,1-dibromoalkenes using a diethyl phosphonate/EtONa/EtOH system

  CX Kuang, H Senboku, M Tokuda TETRAHEDRON 58 (8) 1491 -1496 2002年02月 [査読無し][通常論文]
   

  (E)-Vinyl bromides were readily prepared from 1,1-dibromoalkenes by microwave irradiation within 1 min using a diethyl phosphonate/EtONa/EtOH system. This method utilizes cheap and environmentally friendly reagents, requires only a short reaction time, and gives (E)-vinyl bromides in high stereoselectivities and high yields. (C) 2002 Elsevier Science Ltd. All rights reserved.
• Stereoselective preparation of 7-exo-amino-7-endo-substituted bicyclo[4.1.0]heptanes

  MA Chowdhury, H Senboku, M Tokuda, T Chiba TETRAHEDRON 58 (9) 1673 -1677 2002年02月 [査読無し][通常論文]
   

  Bicyclo[4.1.0]heptan-7-one N,O-hemiacetals undergo substitution reaction with Wittig reagents (Ph3P==CHR3) to give stereoselectively the corresponding 7-exo-amino-7-endo-substituted bicyclo[4.1.0]heptanes in good yields. (C) 2002 Elsevier Science Ltd. All rights reserved.
• Convenient synthesis of cyclic alpha-alkoxyl-alpha,beta-unsaturated carboxylic acids by nickel-catalyzed electrochemical carboxylation of lactone enol triflates

  H Senboku, H Kanaya, M Tokuda SYNLETT (1), 140-142 (1) 140 -142 2002年01月 [査読無し][通常論文]
   

  Electrochemical carboxylation of lactone enol triflates in DMF containing a catalytic amount of NiBr2.bpy with a platinum cathode and a magnesium anode under an atmospheric pressure of CO2 gave the corresponding cyclic alpha-alkoxyl-alpha,beta-unsaturated carboxylic acids, captodative cycloalkenes, in good yields.
• A facile synthesis of ring-fused alkylidenecyclopropanes by olefination reaction of bicyclo[n.1.0]alkanone N,O-hemiacetals with Wittig reagents

  MA Chowdhury, H Senboku, M Tokuda, Y Masuda, T Chiba TETRAHEDRON LETTERS 42 (40) 7075 -7078 2001年10月 [査読無し][通常論文]
   

  Ring-fused alkylidenecyclopropanes. bicyclo[n.1.0]alkylidene derivatives, were readily synthesized by olefination reaction of bicyclo[n.l.0]alkanone N,O-hemiacetals with Wittig reagents in good yields. (C) 2001 Elsevier Science Ltd. All rights reserved.
• Stereochemical study on electrochemical carboxylation of vinyl triflates

  H Senboku, H Kanaya, Y Fujimura, M Tokuda JOURNAL OF ELECTROANALYTICAL CHEMISTRY 507 (1-2) 82 -88 2001年07月 [査読無し][通常論文]
   

  A stereochemical study on electrochemical carboxylation of ethoxycarbonyl- or phenyl-substituted vinyl triflates was carried out. Vinyl triflates in DMF with a platinum cathode and a magnesium anode underwent electrochemical carboxylation with retention of their geometries to give the corresponding alpha,beta -unsaturated carboxylic acids in moderate to good yields. The stereochemical outcome of these electrochemical carboxylations is discussed by comparison with predominant formation of a (Z)-isomer from either (E)- or (Z)-vinyl bromides. (C) 2001 Elsevier Science B.V. All rights reserved.
• Convenient and stereoselective synthesis of (Z)-1-bromo-1-alkenes by microwave-induced reaction

  CX Kuang, H Senboku, M Tokuda TETRAHEDRON LETTERS 42 (23) 3893 -3896 2001年06月 [査読無し][通常論文]
   

  (Z)-l-Bromo-l-alkenes were stereoselectively prepared in high yields in a short reaction time (0.2 1.0 min) by microwave irradiation of the corresponding 2,3-dibromoalkanoic acids in DMF in the presence of triethylamine. (C) 2001 Elsevier Science Ltd. All rights reserved.
• Efficient electrochemical dicarboxylation of phenyl-substituted alkenes: Synthesis of 1-phenylalkane-1,2-dicarboxylic acids

  H Senboku, H Komatsu, Y Fujimura, M Tokuda SYNLETT (3), 418-420 (3) 418 -420 2001年03月 [査読無し][通常論文]
   

  Electrochemical dicarboxylation of phenyl-substituted alkenes in the presence of atmospheric pressure of carbon dioxide with a platinum plate cathode and a magnesium rod anode readily took place efficiently in a DMF solution containing 0.1 M Et4ClO4 to give the corresponding 1,2-dicarboxylic acids in high yields.
• Stereoselective synthesis of (E)-beta-arylvinyl halides by microwave-induced Hunsdiecker reaction

  CX Kuang, H Senboku, M Tokuda SYNLETT (10), 1439-1442 (10) 1439 -1442 2000年10月 [査読無し][通常論文]
   

  (E)-beta-Arylvinyl halides were prepared in high yields in a short reaction (1-2 min) by microwave irradiation of the corresponding 3-arylpropenoic acids in the presence of N-halosuccinimide and catalytic LiOAc.
• 超臨界二酸化炭素中での電気化学的手法による有機合成

  仙北 久典, 徳田 昌生 Jasco report 42 1 -6 2000年08月
• Exclusive 1,4-aryl migration in a stereoselective cyclization of N-benzylalk-4-enylaminyl radicals

  H Senboku, H Hasegawa, K Orito, M Tokuda TETRAHEDRON LETTERS 41 (30) 5699 -5703 2000年07月 [査読無し][通常論文]
   

  Tandem cyclization of N-benzylalk-4-enylaminyl radicals readily occurs to give 1,4-aryl migration pyrrolidines, trans-N-methyl-2-alkyl-5-(1-phenylalkyl)pyrrolidines, exclusively. (C) 2000 Elsevier Science Ltd. All rights reserved.
• Divergent electrochemical carboxylation of vinyl triflates: new electrochemical synthesis of phenyl-substituted alpha,beta-unsaturated carboxylic acids and aliphatic beta-keto carboxylic acids

  H Senboku, Y Fujimura, H Kamekawa, M Tokuda ELECTROCHIMICA ACTA 45 (18) 2995 -3003 2000年 [査読無し][通常論文]
   

  Electrochemical carboxylation of vinyl triflates using a magnesium anode, as a reactive metal electrode, was investigated. Alkyl-substituted vinyl triflates were electrolyzed in the presence of an atmospheric pressure of carbon dioxide to give beta-keto carboxylic acids as a sole products. On the other hand, electrochemical carboxylation of phenyl-substituted vinyl triflates gave alpha,beta-unsaturated carboxylic acids exclusively. These divergent electrochemical carboxylation resulted from chemoselective cleavage of O-S or C-O bond of vinyl triflate, which was affected by the presence or absence of phenyl substituents in the structure of starting vinyl triflates. (C) 2000 Elsevier Science Ltd. All rights reserved.
• Tandem cyclization of N-allylaminyl radicals: Stereoselective synthesis of 1,2,5-trisubstituted pyrrolizidines

  H Senboku, Y Kajizuka, H Hasegawa, H Fujita, H Suginome, K Orito, M Tokuda TETRAHEDRON 55 (21) 6465 -6474 1999年05月 [査読無し][通常論文]
   

  Radical reaction of N-allylalk-4-enylaminyl radicals, generated from the corresponding N-chloroamines by treatment with Bu3SnH-AIBN in refluxing toluene, was carried out. Tandem cyclization of the resulting neutral aminyl radicals readily took place stereoselectively to give 1,2,5-trisubstituted pyrrolizidines and a pyrroloindole derivative as a sole product in good yields. The cyclization products contained only two stereoisomers in each reaction, indicating that both of the consecutive cyclizations proceeded in a stereoselective manner. (C) 1999 Elsevier Science Ltd. All rights reserved.
• New stereoselective synthesis of (+/-)-trans-2-butyl-5-heptyl-1-methylpyrrolidine, ant venom alkaloid, by aminyl radical cyclization

  H Senboku, H Hasegawa, K Orito, M Tokuda HETEROCYCLES 50 (1) 333 -340 1999年01月 [査読無し][通常論文]
   

  New synthesis of (+/-)-trans-2-butyl-5-heptyl-1-methylpyrrolidine (1), ant venom alkaloid, was achieved by the use of stereoselective cyclization of aminyl radicals. Thus, orthoester Claisen rearrangement of 1-hexen-3-ol (2) gave (E)-ethyl 4-octenoate (3). Reaction of ester (3) with 2-methylaminopyridine and AlCl3 afford ed the corresponding N-methyl-N-(2-pyridyl)amide (4), which was treated with heptylmagnesium iodide at -78 degrees C to give (E)-4-pentadecen-8-one (5). Reductive amination of ketone (5) with methylamine gave N-methyl-1-heptyl-4-octenylamine (6). Treatment of amine (6) with NCS in toluene gave the corresponding N-chloroamine (12), and successive heating under reflux with Bu3SnH and AIBN resulted in stereoselective cyclization of the aminyl radical to give (+/-)-trans-2-butyl-5-heptyl-1-methylpyrrolidine (1) in a 59% yield. Similarly, 1-nonen-3-ol (7) was converted into N-methyl-1-butyl-4-undecenylamine (11), which was subjected to the aminyl radical cyclization to give 1 in a 49% yield.
• New electrochemical carboxylation of vinyl triflates. Synthesis of beta-keto carboxylic acids

  H Kamekawa, H Senboku, M Tokuda TETRAHEDRON LETTERS 39 (12) 1591 -1594 1998年03月 [査読無し][通常論文]
   

  Electrochemical reduction of alicyclic vinyl triflates (1a-1e) in a DMF solution containing 0.1 M Bu4NBF4 under an atmospheric pressure of carbon dioxide with a platinum cathode and a magnesium anode resulted in the cleavage of an oxygen-sulfur bond of 1 to give the corresponding beta-keto carboxylic acids (2a-2e) in yields of 28-77%. (C) 1998 Elsevier Science Ltd. All rights reserved.
• New and convenient synthesis of 3-methylenepent-4-enoic acid by electrochemical carboxylation

  M Tokuda, A Yoshikawa, H Suginome, H Senboku SYNTHESIS-STUTTGART (10),1143-1145 (10) 1143 -& 1997年10月 [査読無し][通常論文]
   

  Electrochemical carboxylation of 2-bromomethyl-1,4-dibromobut-2-ene (1) with atmospheric carbon dioxide in a DMF solution containing Bu4NI with a platinum cathode and a manganin or nickel anode gave 3-methylenepent-4-enoic acid (3) in 57 % yield. The acid 3 can be used as a diene in an aqueous intermolecular Diels-Alder reaction with dimethyl fumarate to give the adduct 7 in 67 % yield.
• Facile synthesis of aryl-substituted 2-alkenoic acids by electroreductive carboxylation of vinylic bromides using a magnesium anode

  H Kamekawa, H Senboku, M Tokuda ELECTROCHIMICA ACTA 42 (13-14) 2117 -2123 1997年 [査読無し][通常論文]
   

  Electrochemical carboxylation of phenyl-substituted vinylic bromides in the presence of atmospheric carbon dioxide using a platinum cathode and a magnesium anode gave the corresponding alpha,beta-unsaturated carboxylic acids in 63-92% isolated yields. A precursor of ibuprofen, 2-(pisobutylphenyl)propenoic acid, was readily obtained in a 93% yield by a similar electrochemical carboxylation of 1-bromo-1-(p-isobutylphenyl)ethene. Stereochemical studies showed that thermodynamically less stable Z-isomers were preferentially produced from either E- or Z-vinylic bromides in these electrochemical carboxylations. (C) 1997 Elsevier Science Ltd.
• Synthesis of alpha,beta-unsaturated carboxylic acids by nickel(II)-catalyzed electrochemical carboxylation of vinyl bromides

  H Kamekawa, H Kudoh, H Senboku, M Tokuda CHEMISTRY LETTERS (9),917-918 (9) 917 -918 1997年 [査読無し][通常論文]
   

  Electrochemical carboxylation of alkyl-substituted vinyl bromides (1a-1g) in the presence of 20 mol% of NiBr2.bpy under an atmospheric pressure of carbon dioxide with a platinum cathode and a magnesium anode gave the corresponding alpha,beta-unsaturated carboxylic acids (2a-2g) in yields of 53-82%.
• Photoinduced molecular transformations .159. Formation of some furonaphthyridinones by selective beta-scission of cyclobutanoxyl radicals generated from [2+2] photoadducts of 4-hydroxy-1-phenyl [1,8] naphthyridin-2(1H)-one with alkenes

  H Senboku, M Takashima, M Suzuki, K Kobayashi, H Suginome TETRAHEDRON 52 (17) 6125 -6138 1996年04月 [査読無し][通常論文]
   

  The [2+2] photoaddition of 4-hydroxy-1-phenyl[1,8]naphthyridin-2(1H)-one 7 with various alkenes in methanol gave regioselectively the corresponding head-to-tail adducts (8,9, and 11). The photolysis of the hypoiodites generated by the in situ reaction of the cyclobutanol adducts 8,9, and 11 with excess mercury(II) oxide-iodine reagent in benzene induced a regioselective scission of their non-ring junction bond of the corresponding alkoxyl radicals to give substituted 3,9-dihydro-9-phenylfuro[2,3-b][1,8]naphthyridin-4(2H)-one (12 and 15) and/or substituted 3,5-dihydro-5-phenylfuro[3,2-c][1,8]naphthyridin-4-(2H)-one (13,14, and 16). An unusual byproduct 12a was formed in the photolysis of the hypoiodite of the [2+2] photoadduct 8a of 4-hydroxy-1-phenyl[1,8]naphthyridin-2-(1H)-one with isobutene. (C) 1996 Elsevier Science Ltd.
• PHOTOINDUCED MOLECULAR-TRANSFORMATIONS .147. [2+2] PHOTOADDITION OF PROTECTED 4-HYDROXY-1(2H)-ISOQUINOLINONE WITH AN ELECTRON-DEFICIENT ALKENE AND THE FORMATION OF A 3,6-EPOXY-3,4,5,6-TETRAHYDRO-2-BENZAZOCIN-1(2H)-ONE VIA A BETA-SCISSION OF CYCLOBUTANOXYL RADICALS GENERATED FROM THE RESULTING PHOTOADDUCT

  H SUGINOME, Y KAJIZUKA, M SUZUKI, H SENBOKU, K KOBAYASHI HETEROCYCLES 37 (1) 283 -288 1994年01月 [査読無し][通常論文]
   

  The direct irradiation of 4-benzyloxycarbonyloxy-2-methyl-1(2H)-isoquinolinone gave a 1 to 1 ratio of two stereoisomers of [2+2] photoadducts in 97% yield. Removal of the protecting group from the adducts by hydrogenolysis gave the corresponding cyclobutanols, (1 alpha, 2a alpha, 8b alpha)-(+/-)-1-cyano-1,2a,3,8b-tetrahydro-8 b-hydroxy-3 -methylcyclobut[c]-isoquinolin-4(2H)-one and its (1 alpha, 2a beta, 8b beta)- isomer in 78 and 67% yields. The photolysis of the hypoiodite generated in situ from the (1 alpha, 2a alpha, 8b alpha)-(+/-)-cyclobutanol with mercury(II) oxide - iodine in benzene induced a regioselective beta-scission at the ring fusion bond of the cyclobutanoxyl radical to give 5-cyano-3,6-epoxy-3,4,5,6-tetrahydro-6-hydroxy-2-methyl-2- benzazocin-1(2H)-one in 76% yield. The cyano substituent and the amide nitrogen play a decisive role in directing the bond to be cleaved.

特許

• 置換スチレン誘導体

  JP2001081066
• Substituted Styrene Derivative

  JP2001081066

受賞

• 2006年 有機電気化学研究会奨励賞
  
• 2004年 日本化学会北海道支部奨励賞
  
• 2004年 Award for Young Chemist, Hokkaido Branch of The Chemical Society of Japan
  

共同研究・競争的資金等の研究課題

• 二酸化炭素を炭素源とするβ－アミノ酸の金属フリーな環境調和型電解合成

  日本学術振興会：科学研究費助成事業

  研究期間 : 2022年04月 -2025年03月 

  代表者 : 仙北 久典
• 二酸化炭素を炭素源として用いる電子移動型極性変換によるマンデル酸の環境調和型合成

  研究期間 : 2016年04月 -2019年03月 

  代表者 : 仙北 久典
• 電子移動還元反応を利用する二酸化炭素とアルコールからの増炭カルボン酸の一段階合成

  日本学術振興会：科学研究費補助金（基盤研究(C)）

  研究期間 : 2013年06月 -2016年03月 

  代表者 : 仙北 久典
• 二酸化炭素と水の分子機能を利用した水共存有機膨張液相における反応促進と選択性制御

  日本学術振興会：科学研究費助成事業

  研究期間 : 2010年 -2012年 

  代表者 : 荒井 正彦, 藤田 進一郎, 仙北 久典

   

  有機液相(反応基質あるいは溶媒),加圧二酸化炭素,水を構成要素とする多相系反応場を水素化反応や光触媒反応に応用して,その有用性を示すとともに二酸化炭素と水の役割・機能を分子レベルで解明した。対象とした反応は,ニトリル化合物からの第1級アミン合成,フェノール水素化,水の光分解による水素製造等である。有機液相に溶解した二酸化炭素分子と基質との相互作用,担持金属触媒と反応化学種(二酸化炭素と水素から生成する一酸化炭素,有機基質,水)との相互作用を赤外分光法(透過法,全反射法)で調べた。本多相系反応場で反応速度の向上,生成物分布の変化,あるいは触媒寿命の変化が見られ,二酸化炭素と水の機能はそれぞれの反応で異なることを示した。
• 電解反応による極性変換-スルホナートを求核剤に用いる炭素-炭素結合生成反応

  文部科学省：科学研究費補助金(基盤研究(C))

  研究期間 : 2003年 -2005年 

  代表者 : 仙北 久典, 福原 彊, 吉田 雅紀, 原 正治, 仙北 久典

   

  3-フェニル-1-プロパノールのトシラートを基質として一室型セル中、陰極に白金板、陽極にマグネシウム棒、DMFを溶媒に用いて定電流電解を行ったが、主生成物として母体のアルコールを与えるのみであった。一方、同基質のメシラートをシクロヘキサノン存在下電解還元すると期待通りの炭素-炭素結合生成反応が進行し、1-(3-フェニルプロピル)-1-シクロヘキサノールを30%程度の収率で得ることに成功した。シクロヘプタノンや他の鎖状ケトンを用いても同様の炭素-炭素結合生成反応が10〜30%の収率で進行することも確認できたが、収率の向上には至らなかった。また、1-ドデカノールのメシラートをビフェニル2当量存在下電解還元すると、ドデカンが42%の収率で得られた。シクロヘキサノンを加えても目的の炭素-炭素結合形成反応は進行せず、ドデカンの収率が向上したのみであった。そこで、メシラートの電解還元反応によるアルカンへの変換について検討を行ったところ、4当量のビフェニルならびに10当量のt-BuOHを共存させて1-ドデカノールのメシラートの電解還元反応を行ったところ、74%の収率でドデカンを得ることができた。本手法を、分子内の適当な位置にアルケン、エポキシド、エステル、エーテル、水酸基、シアノ基などの官能基を有するメシラートに適応したところ、それらの官能基を損なうことなくメシラート部位の還元が選択的に進...
• マイクロウェーブ照射法による環境調和的な合成反応の開発

  文部科学省：科学研究費補助金(萌芽的研究, 萌芽研究)

  研究期間 : 2001年 -2002年 

  代表者 : 徳田 昌生, 仙北 久典, 折登 一彦, 黒野 暢仁

   

  1.(E)-および(Z)-ハロゲン化ビニルの高効率・高立体選択的合成trans-α,β-不飽和カルボン酸の臭素化で得られるanti-2,3-ジブロモアルカン酸にDMF溶媒中トリエチルアミンを添加してマイクロ波を1分間照射すると、相当する(Z)-臭化ビニルが高効率かつ高立体選択的に合成されることをすでに報告した。今年度は、同一の出発原料であるanti-2,3-ジブロモアルカン酸を酢酸中1.2当量の酢酸銀を加えて1分間マイクロ波照射することによって、全く異なる異性体である(E)-臭化ビニルが高収率かつ高立体選択的に合成されるという、極めて興味深い結果を見出した。2.ハロゲン化ビニルの無溶媒合成反応の開発DMF溶媒中でのマイクロ波反応による(Z)-臭化ビニルの合成についてはすでに成功しているが、無溶媒でマイクロ波照射を行っても同様の合成反応が高効率で進行することを見出し、現在展開を図っている。3.クロスカップリング反応の開発anti-2,3-ジブロモアルカン酸のマイクロ波反応で(Z)-臭化ビニルを合成し、そのままone-potでPd触媒、CuIおよびフェニルアセチレンを加えてマイクロ波をさらに2分間照射すると,薗頭カップリングが進行し、相当するエンイン化合物が良好な収率で得られることを見出した。立体選択性の低下が現在のところ問題点である。
• アルケン類の電解ジカルボキシル化による1,2-ジカルボン酸の環境低負荷型合成

  文部科学省：科学研究費補助金(奨励研究(A))

  研究期間 : 2000年 -2001年 

  代表者 : 仙北 久典

   

  研究計画に基づき以下の検討を行い、以下のような実績が得られた。1)シクロヘキセンなどの脂肪族アルケンの電解カルボキシル化については、種々検討を行ったが電解カルボキシル化は進行しなかった。しかしながら、1,3-シクロヘキサジエンなどの環状ジエンを用いるとジカルボキシル化反応が進行し、相当する2-シクロアルケン-1,4-ジカルボン酸を54〜93%の収率で得ることに成功した。さらに、ニッケル触媒を用いるβ-ブロモスチレンの電解ホモカップリング反応は高収率で進行すること、得られるフェニル置換ブタジエンの電解ジカルボキシル化も容易に進行すること、これらの2つの反応がワンポットで行えること等も明らかとした。2)超臨界二酸化炭素を反応媒体としてフェニル置換アルケン類の電解ジカルボキシル化を検討したところ、収率よく相当するジカルボン酸を得ることができ、有機溶媒を用いた反応と比較してもほぼ同様の収率でジカルボン酸が得られることを明らかとした。3)特異な骨格としてメチレンシクロプロパン構造を有するビシクロ[n.1.0]アルキリデン誘導体のアルケン部位に電子吸引性基を有する基質についてジカルボキシル化反応を検討した。その結果、カルボキシル化は容易に進行し、1分子もしくは2分子の二酸化炭素を固定化したモノカルボン酸及びジカルボン酸が基質選択的に生成した。また、得られたカルボン酸はすべてexo-異性体...
• 新規電子移動反応場におけるクロスカップリング反応の開発

  文部科学省：科学研究費補助金(基盤研究(B))

  研究期間 : 1999年 -2001年 

  代表者 : 徳田 昌生, 仙北 久典, 折登 一彦

   

  本研究は、各種ハロゲン化合物とハロゲン化アリールとのクロスカツプリング反応において新規な電子移動場を開発し、温和な条件下効率的かつ選択的に進行する炭素-炭素結合生成反応を開発すること、またそれらの基礎的知見を用いて様々な合成反応に応用することを目的として行われた。主に2種類の電子移動反応場を活用して様々なクロスカップリング反応について検討を行った。ナフタレンをメディエーターとする電解によって高活性亜鉛を調製する新規方法を開発し、それを利用する電子移動反応場では、各種ハロゲン化合物とハロゲン化アリールとのクロスカップリング反応が容易に進行することを見出した。また、この手法を用いることによって、イブプロフェンやナプロキセンをはじめとする非ステロイド系抗炎症剤の前駆体である2-アリールプロペン酸エチルなどのカップリング生成物を高収率で合成することに成功した。一方、反応性金属陽極を用いる電解反応場における反応では、フェナントレンなどのメディエーターの存在下マグネシウムあるいは亜鉛陽極を用いてハロゲン化アリールを電解還元することにより、アリールラジカルを発生させることに成功し、環化生成物を得ることができた。通常のAIBN/Bu_3SnHを用いるラジカル環化反応を利用する生理活性アルカロイド類等の合成についても興味ある成果を得ることができた。また、電解反応場ではビニルトリフラートど二酸化...
• 二酸化炭素の電解固定化による抗炎症剤の合成

  文部科学省：科学研究費補助金(基盤研究(B))

  研究期間 : 1998年 -2000年 

  代表者 : 徳田 昌生, 佐々木 〓美, 仙北 久典, 折登 一彦, 佐々木 皇美

   

  1.抗炎症剤あるいは抗炎症剤前駆体の合成(1)ハロゲン化ビニルの電解カルボキル化-アリール置換臭化ビニルを常圧の二酸化炭素の存在下、白金陰極-マグネシウム陽極を用いて電解することによって、相当する2-アリールプロペン酸を高収率で合成することができた。この手法を用いイブプロフェン、ナプロキセン、ケトプロフェンなどの前駆体の合成に成功した。これらの前駆体は不斉水素化を行うことによって容易に抗炎症剤へ導くことができる。(2)アリールメチルケトンの電解カルボキル化-同様の電解反応によってアリールメチルケトンから抗炎症剤の前駆体である2-アリール-2-ヒドロキシプロパン酸を高収率で合成することができた。本電解手法はロキソプロフェンの合成に極めて有効であった。(3)置換ハロゲン化ベンジルの電解カルボキル化-同様の電解反応によって置換ハロゲン化ベンジルから各種抗炎症剤のラセミ体を高収率で合成した。2.超臨界二酸化炭素中での抗炎症剤の合成超臨界二酸化炭素を反応試薬および溶媒として用いることによって、二酸化炭素を電解固定化し、溶液中の反応より高収率で各種抗炎症を合成することができた。3.電解カルボキシル化を利用した有用なカルボン酸の合成抗炎症剤合成に関連して、ビニルトリフラートおよびフェニル置換アルケンの電解カルボキシル化を行い、α,β-不飽和カルボン酸、β-ケトカルボン酸および2-フェニルコ...
• 超臨界二酸化炭素を用いる電解カルボキシル化反応の開発と抗炎症剤合成への応用

  文部科学省：科学研究費補助金(奨励研究(A))

  研究期間 : 1998年 -1999年 

  代表者 : 仙北 久典

   

  昨年度の研究では、少量のアセトニトリルを共溶媒として用いると超臨界二酸化炭素中(反応温度40℃、二酸化炭素圧力80Kg/cm^2)でも電解に十分な通電が得られることを見出し、本反応を用いて抗炎症剤イブプロフェン[2-(4-イソブチルフェニル)プロピオン酸]の合成にも成功した。今年度はさらに様々な出発物質から種々の抗炎症剤ならびにそれらの前駆体の合成を行った。相当する塩化ベンジルまたは芳香族置換臭化ビニルを基質として用いる超臨界二酸化炭素中での電解カルボキシル化では、抗炎症剤であるイブプロフェン、ナプロキセン、シクロプロフェンならびにそれらの光学活性体の前駆体を良好な収率で得ることができた。一方、相当するアリールメチルケトンを基質として同様の反応を行うと2-アリールプロパン酸構造を有する抗炎症剤の光学活性体の前駆体であるα-ヒドロキシカルボン酸を高収率で合成することができた。なかでも、ロキソプロフェンはその分子内に脂肪族ケトン構造を有しており、共存するケトンのうち芳香族ケトン部のみを化学選択的にカルボキシル化できるのは電解反応の特長を生かしたものといえる。これらの結果は、日本化学会題78春季年会において発表予定であり、今後学術論文として投稿する予定である。一方、臭化ビニルの類縁体としてビニルトリフラートがあげられる。含フッ素化合物は超臨界二酸化炭素に高い溶解性を示すことが知られ...
• 環境調和型共有結合生成反応-超臨界流体およびKを溶媒とする新規反応場の開発

  文部科学省：科学研究費補助金(特定領域研究(A))

  研究期間 : 1998年 -1998年 

  代表者 : 徳田 昌生, 高橋 憲司, 仙北 久典

   

  1.超臨界二酸化炭素中での電解カルボキシル化白金陰極、マグネシウム陽極を取り付けた高圧反応容器に支持電解質としてBu_4NBF_4、共溶媒として少量のアセトニトリル(10ml:155mlの反応容器に対して6vol%)を加え、二酸化炭素の臨界点以上の反応条件(40℃,80Kg/cm^2)で電解することによって、電解力ルボキシル化が可能となることを見出した。超臨界二酸化炭素中での電解によるカルボン酸の合成は本研究が世界で最初の例である。さまざまな置換ハロゲン化アリールを電解すると相当するアレーンカルボン酸が高収率で得られた。例えば、1-および2-クロロナフタレンからナフタレン手およびナフタレン-2-カルボン酸をそれぞれ92%および83%の収率で得ることができた。また、ハロゲン化ベンジル類を同様な条件下電解することによって置換フェニル酢酸を高収率で合成することができた。現在、さらにさまざまな基質を用いて電解カルボキシル化を検討している。2.超臨界二酸化炭素を用いる抗炎症剤の合成1-クロロ-1-(4-イソブチルフェニル)エタンおよび1-クロロ-(6-メトキシナフチル)エタンを超臨界二酸化炭素中上記の条件で電解することによって、抗炎症剤であるイブプロフェンおよびナプロキセンをそれぞれ79%および74%の収率で合成することに成功した。3.電子移動反応における超臨界流体の特性に関する研究超...
• 超臨界二酸化炭素を用いる有機電解合成

  文部科学省：科学研究費補助金(萌芽的研究)

  研究期間 : 1997年 -1998年 

  代表者 : 徳田 昌生, 佐々木 皇美, 仙北 久典

   

  1. 超臨界二酸化炭素中での電解カルボキシル化平成9年度の研究において、白金陰極、マグネシウム陽極を取り付けた高圧反応容器に支持電解質としてBu_4NBF_4、共溶媒として少量のアセトニトリル(10ml;155mlの反応容器に対して6vol%)を加え、臨界点以上の反応条件(40℃,80Kg/cm^2)にすると電解が可能となることを見出した。今年度は1-プロモナフタレンを基質として用い、反応条件についてさらに詳細な検討を行った。その結果、基質1mmolに対して5mmolのBUu4NBF_4の支持電解質を用い、5F/molの通電量で電解することによって95%の収率でナフタレン-1-カルボン酸を得ることができた。共溶媒については3mlまで減らしても約70%の収率でカルボン酸が得られることを見出した。超臨界二酸化炭素中での電解によるカルボン酸の合成は本研究が世界で最初の例である。2. 芳香族カルボン酸の合成少量のアセトニトリルを共溶媒とし超臨界二酸化炭素中上記の条件下1-クロロナフタレンを20mA/cm^2の定電流で電解することによって、ナフタレン-1-カルボン酸を92%の高収率で得ることができた。さまざまなハロゲン化アリールを同様の条件下電解することによって括弧内に示す収率でそれぞれ相当するカルボン酸を合成することができた:2-クロロナフタレン(83%)、2-ブロモナフタレン(79...
• 流動層反応電極を利用する二酸化炭素の固定-有用な有機カルボン酸の合成

  文部科学省：科学研究費補助金(試験研究(B), 基盤研究(A))

  研究期間 : 1995年 -1997年 

  代表者 : 徳田 昌生, 佐々木 皇美, 千葉 忠俊, 仙北 久典, 折登 一彦

   

  本研究は電解を利用して常圧の二酸化炭素を各種の有機基質に固定化することによって有用な有機カルボン酸を合成することを目的として行われたものである。成果の概要を以下に述べる。1.反応性電極を用いる電解カルボキシル化による不飽和カルボン酸の合成-常圧の二酸化炭素の存在下マグネシウムの反応性電極を用いて電解することによって、γ-置換ハロゲン化アリルからγ-置換-β,γ-不飽和カルボン酸、ハロゲン化ビニルからα,β-不飽和カルボン酸、ハロゲン化プロパルギルから1,2-アルカジエン酸、1,4-ジブロモ-2-ブロモメチル-2-ブテンから3-メチレン-4-ペンテン酸、ビニルトリフラートからβ-ケトカルボン酸をいずれも位置選択的および高収率で合成することができた。2.抗炎症剤の高効率的合成-1で得られた成果を基としてIbuprofen、Naprpxen、Flurbiprofen、Cicloprofen、Ketoprofen等の抗炎症剤の前駆体であるα,β-不飽和カルボン酸を高収率で合成することに成功した。高エナンチオ選択的な水素化反応がすでに知られているので、本電解カルボキシル化は抗炎症剤の合成法としてきわめて有用であることを明らかにした。3.流動層電解装置を用いる電解カルボキシル化-流動層電解装置を試作し、臭化シンナミルの電解カルボキシル化を例にとって二酸化炭素の流量、反応温度、通電量、電流...
• 電解調製の活性亜鉛を用いる新しい有機反応の開発

  文部科学省：科学研究費補助金(重点領域研究)

  研究期間 : 1995年 -1995年 

  代表者 : 徳田 昌生, 仙北 久典, 折登 一彦

   

  1.電解調製の活性亜鉛のキャラクタリゼーションDMF溶液中白金陰極-亜鉛陽極を用いて電解することにより活性な亜鉛が簡便に調製できることをすでに見出しているが、この電解調製亜鉛(EGZn)について走査型電子顕微鏡(FE-SEM)、X線回折、光電子分光分析(XPS)、蛍光X線分析および表面積測定などによってキャラクタリゼーションを行った。その結果、EGZnは0.1μ以下の亜鉛微粒子の凝集体で、PbやClあるいはN原子を含まない純度の高い結晶であり、その表面積は他の市販金属亜鉛より数10〜数100倍大きいことを明らかにすることができた。この極めて大きな表面積がEGZnの高活性の原因のひとつであることが判明した。2.電解調製活性亜鉛(EGZn)を用いる有機合成反応イソプレンから容易に合成できる2-ブロモメチル-1,4-ジブロモ-2-ブテン(BMDBB)をEGZnの存在下アルデヒドやケトンと反応させることにより温和な条件でイソプレニル化アルコールが高収率で得られることを見出している。この条件下において二酸化炭素との反応は進行しなかったが、常圧の二酸化炭素の存在下BMDBBを電解還元することによりイソプレンカルボン酸を合成することができた。一方、EGZnの存在下ハロゲン化アリルをケトンやアルデヒドあるいは酸無水物と反応させることにより温和な条件下でアリル化を進行させることができ、それぞれ...
• 複素環化合物の新規合成法の開発と生理活性分子合成への応用

  文部科学省：科学研究費補助金(奨励研究(A))

  研究期間 : 1994年 -1994年 

  代表者 : 仙北 久典

   

  研究計画に基づき、まず文献既知である4-ヒドロキシ-2-フェニル[1,8]ナフチリジン-2(1H)-オンとイソブテンをメタノール中500W高圧水銀灯によりPyrexフィルターを通して光照射し、head to headの位置選択的[2+2]光シクロ付加反応によりシクロブタノール誘導体を高収率で得た。エチルビニルエーテル、1-メトキシシクロヘキセン、酢酸イソプロペニルを用いた場合も同様の付加反応により相当するシクロブタノール誘導体を50-80%の収率で得た。次に、得られたシクロブタノールをベンゼン中、各3等量の酸化水銀およびヨウ素存在下、Pyrexフィルターを通し光照射を行った。その結果、発生したアルコキシルラジカルの炭素-炭素結合での位置選択的β-開裂反応によりフロナフチリジンが38-74%の収率で生成することを見出した。イソブテンとの付加体であるシクロブタノールからはフロ[2,3-b][1,8]ナフチリジン-4[2H]-オン誘導体のみが得られた。一方、エチルビニルエーテルおよび1-メトキシシクロヘキセンとの付加体であるシクロブタノールからは、フロ[3,2-c][1,8]ナフチリジン-4[2H]-オンのみが得られ、酢酸イソプロペニルとの付加体であるシクロブタノールからは両方のフロナフチリジン誘導体が得られた。フロナフチリジン骨格を有する化合物は抗アレルギー性・抗炎症性・鎮咳作用...
• 新しい選択的有機化学プロセスの開発と生理活性分子の高効率合成への応用に関する研究

  文部科学省：科学研究費補助金(一般研究(A))

  研究期間 : 1991年 -1993年 

  代表者 : 杉野目 浩, 小林 和裕, 折登 一彦, 徳田 昌生, 仙北 久典

   

  1 有機合成に有用なキノンの新光付加反応の開発-2-ヒドロキシン、2-アミノ、または2-メルカプトナフトキノンと種々のオレフィンとの新奇[3+2]光付加反応を見い出し、該反応によりマチュリノン、キナマイシン骨格、イソタンシノン骨格等の新合成を達成した。また2-アリールアミノ-、2-アルキルアミノナフトキノンの光アルキルならびに光アシル化反応など有機合成化学に有用な新プロセスを開発した。2 ROIの光分解により発生せしめたアルコキシルラジカルの選択的ベータ開裂反応を利用する有機合成法の開発-標記開裂反応をキーステップとするビシクロ[5.4.0]ウンデカン骨格の一般合成法、含酸素複素環の一般合成法、フタリド類、γ-ならびにδ-ラクトンの合成法等を開発した。これらの方法を用いて(±)-カリオフィレン、(±)-イソカリオフィレン、(±)-ヒマチャレンなどのセスキテルペン、(±)-ルシフェイオリドなどのマクロリド、(±)-オイデスミン、(±)-ピペリトール、(±)-ヤンガンビンなどの天然リグナンの全合成を達成した。3 オキシム類の光による新分子変換-多数のステロイド系α,β-不飽和ケトンオキシムを新たに合成し、β,γ-不飽和ケトンオキシムへの光異性化、立体特異的メタノール付加などの新たな反応を見い出し、構造の生成物の相関を明らかにした。4 不飽和アミンの環化による2,5-ジ置換ピロリジ...
• Deveropment of synthetic organic reactions by using hypervalent iodine compounds
• Synthesis of Carboxylic Acid by the Electrochemical Carboxylation using A Reactive-metal Anode.
• Electro-organic synthesis

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