MAEGAWA Tomohiro

Researcher Information

Degree

• doctor(Pharmacology)（Osaka University）

URL

https://jglobal.jst.go.jp/detail?JGLOBAL_ID=200901060608155601

ORCID ID

•  https://orcid.org/0000-0003-1580-1110

J-Global ID

• 200901060608155601

Research Interests

• 環境調和型反応   複素環   有機合成化学   catalytic reaction   synthetic organic chemistry   

Research Areas

• Life sciences / Pharmaceuticals - chemistry and drug development

Academic & Professional Experience

• 2019/04 - Today  School of Pharmaceutical SciencesLaboratory of Medicinal Chemistry, School of Pharmaceutical SciencesProfessor
• 2013/04 - 2019/03  Kindai UniversitySchool of Pharmaceutical SciencesAssociate Professor
• 2009/01 - 2013/03  Osaka UniversityGraduate School of Pharmaceutical SciencesSpecial-Appointed Associate Professor
• 2007/10 - 2008/12  Gifu Pharmaceutical UniversityLaboratory of Medicinal ChemistryLecturer
• 2007/04 - 2007/09  Gifu Pharmaceutical UniversityLaboratory of Medicinal ChemistryAssistant Professor
• 2003/04 - 2007/03  Gifu Pharmaceutical UniversityLaboratory of Medicinal ChemistryAssistant Professor

Education

•        - 2003  Osaka University  薬学研究科  分子薬科学専攻
•        - 2003  Osaka University  Graduate School, Division of Pharmaceutical Sciences
•        - 1998  Nagoya University  School of Engineering  応用化・物質化学科
•        - 1998  Nagoya University  Faculty of Engineering

Association Memberships

• ヨウ素学会   日本プロセス化学会   有機合成化学協会   アメリカ化学会   日本薬学会   The Society of Synthetic Organic Chemistry, Japan   The Pharmaceutical Society of Japan   

Published Papers

• n-Bu4NI/H2O2-catalyzed mild conversion of hydroxamic acids to carboxylic acids

  Akira Nakamura; Jyunya Morimoto; Maho Taniguchi; Haruka Aoyama; Jiadong He; Tomohiro Maegawa

  Tetrahedron Letters Elsevier BV 126 154656 - 154656 0040-4039 2023/08
• Regioselective Synthesis of 3,4-Disubstituted Isoxazoles by Using a Chalcone-Rearrangement Strategy

  Tomohiro Maegawa; Akira Nakamura; Tohko Kine; Haruna Uenishi; Yuri Maki; Yasuhito Kase; Mayo Takagi

  Synlett Georg Thieme Verlag KG 34 (11) 1253 - 1258 0936-5214 2023/02 

  Abstract We have developed a regioselective synthesis of 3,4-disubstituted isoxazoles by using a chalcone-rearrangement strategy. The reaction of β-ketoacetals with hydroxylamine hydrochloride and pyridine afforded the corresponding 3,4-disubstituted isoxazoles via isoxazolines or oximes. Depending on the substrate, another disubstituted isomer was also obtained under our optimized conditions, and a reaction mechanism for each transformation is proposed.
• A concise synthesis of thioaurones via NBS-induced cyclization of MOM-protected 2′-mercaptochalcones

  Akira Nakamura; Fei Rao; Kazuchika Ukiya; Riko Matsunaga; Shin-ichiro Ohira; Tomohiro Maegawa

  Organic & Biomolecular Chemistry Royal Society of Chemistry (RSC) 21 (6) 1134 - 1137 1477-0520 2023 

  Herein we present a simple and efficient method for the synthesis of thioaurones (hemithioindigos) from MOM-protected 2′-mercaptochalcones with NBS and pyridine.
• The Reaction of Ketoximes with Hypervalent Iodine Reagents: Beckmann Rearrangement and Hydrolysis to Ketones

  Tomohiro Maegawa; Yasuyoshi Miki; Ryohei Oishi; Ayumi Maekawa; Kazutoshi Segi; Hiromi Hamamoto; Akira Nakamura

  Synthesis Georg Thieme Verlag KG 54 (18) 4095 - 4103 0039-7881 2022/09 

  Abstract We investigated the reaction of ketoximes with hypervalent iodine reagents. A combination of PhI(OAc)2 and BF3·Et2O promoted the Beckmann rearrangement of ketoximes, thus yielding the corresponding amides. From a detailed investigation of the reaction, we determined that the Beckmann rearrangement is preceded by acetylation of the hydroxy group of the ketoxime in situ, accelerating the Beckmann rearrangement. We confirmed that the acetylated ketoxime undergoes the Beckmann rearrangement with BF3·Et2O. The reaction of ketoximes with Koser’s reagent [PhI(OH)OTs] in the presence of tetrahydrofuran results in hydrolysis, affording the corresponding ketones in high yields at room temperature.
• Selective synthesis of 3-formylbenzofuran and 3-acylbenzofuran using a chalcone rearrangement strategy

  Akira Nakamura; Akira Imamiya; Yuichiro Ikegami; Fei Rao; Harumi Yuguchi; Yasuyoshi Miki; Tomohiro Maegawa

  RSC Advances Royal Society of Chemistry (RSC) 12 (47) 30426 - 30431 2022 

  A method for the highly selective synthesis of two benzofuran isomers, 3-formylbenzofurans and 3-acylbenzofurans, by rearranging and subsequently transforming 2-hydroxychalcones has been developed.
• One-pot Synthetic Approaches for the Construction of Isochroman-4-ones and Benzoxazin-3-ones Using O,P-Acetals

  Akira Nakamura; Kouhei Yamamoto; Ryo Murakami; Norihito Kawashita; Kouichi Matsumoto; Tomohiro Maegawa

  Synthesis Georg Thieme Verlag KG 53 (20) 3862 - 3868 0039-7881 2021/06 [Refereed]
   

  A method for synthesizing six-membered heterocyclic compounds was developed based on the features of O,P-acetals. Sequential reactions of intramolecular cyclization between the methylene carbon atom of O,P-acetal and its electrophilic functional group (ester or protected carbamate) was followed by Horner-Wadsworth-Emmons (HWE) olefination with various aldehydes. The developed one-pot method yielded isochroman-4-one and benzoxazin-3-one derivatives with an alkylidene moiety.
• Chemo- and enantioselective hetero-coupling of hydroxycarbazoles catalyzed by a chiral vanadium(v) complex

  Makoto Sako; Keigo Higashida; Ganesh Tatya Kamble; Kevin Kaut; Ankit Kumar; Yuka Hirose; Da-Yang Zhou; Takeyuki Suzuki; Magnus Rueping; Tomohiro Maegawa; Shinobu Takizawa; Hiroaki Sasai

  Organic Chemistry Frontiers Royal Society of Chemistry (RSC) 8 (17) 4878 - 4885 2021 [Refereed]
   

  The catalytic enantioselective oxidative hetero-coupling of arenols using a chiral vanadium(v) complex has been developed.
• Deprotection of the Carbazole PMB Group Using Hypervalent Iodine Reagent Combined with N-Hydroxyphthalimide

  Tomohiro Maegawa; Kana Yoshikawa; Takanori Tabata; Kazuma Fujimura; Natsumi Kuraoka; Akira Nakamura; Yasuyoshi Miki

  HETEROCYCLES The Japan Institute of Heterocyclic Chemistry 103 (2) 1031 - 1031 0385-5414 2021 [Refereed]
  
• An Improved and Practical Method for Synthesizing of α-Sanshools and Spilanthol

  Akira Nakamura; Kazuki Mimaki; Ken-ichi Tanigami; Tomohiro Maegawa

  Frontiers in Chemistry Frontiers Media SA 8 Article 187  2020/03 [Refereed]
  
• Aromatic Halogenation Using N-Halosuccinimide and PhSSiMe3 or PhSSPh

  Yuuka Hirose; Mirai Yamazaki; Misa Nogata; Akira Nakamura; Tomohiro Maegawa

  The Journal of Organic Chemistry American Chemical Society (ACS) 84 (11) 7405 - 7410 0022-3263 2019/06
• Dehydroxymethyl Bromination of Alkoxybenzyl Alcohols by Using a Hypervalent Iodine Reagent and Lithium Bromide

  Shibata, Ayako; Kitamoto, Sara; Fujimura, Kazuma; Hirose, Yuuka; Hamamoto, Hiromi; Nakamura, Akira; Miki, Yasuyoshi; Maegawa, Tomohiro

  Synlett 29 2275 - 2278 2018/08 [Refereed]
  
• Constraction of azaisoflavone derivatives by hypervalent iodine reagent-mediated oxidative rearrangement of 2'-nitrochalcone

  Akira Nakamura; Reo Takane; Junki Tanaka; Junya Morimoto; Tomohiro Maegawa

  Heterocycles 97 785 - 792 2018/05 [Refereed]
  
• Direct Synthesis of Chalcones from Anilides with Phenyl Vinyl Ketones by Oxidative Coupling through C-H Bond Activation

  Maegawa, Tomohiro; Mizui, Ryota; Urasaki, Miki; Fujimura, Kazuma; Nakamura, Akira; Miki, Yasuyoshi

  ACS Omega 3 5375 - 5381 2018/05 [Refereed]
  
• Hypervalent Iodine-Mediated Beckmann Rearrangement of Ketoximes

  Oishi, Ryohei; Segi, Kazutoshi; Hamamoto, Hiromi; Nakamura, Akira; Maegawa, Tomohiro; Miki, Yasuyoshi

  Synlett 29 1465 - 1468 2018/03 [Refereed]
  
• A mild method for synthesizing carboxylic acids by oxidation of aldoximes using hypervalent iodine reagents

  Akira Nakamura; Hodaka Kanou; Junki Tanaka; Akira Imamiya; Tomohiro Maegawa; Yasuyoshi Miki

  Organic and Biomolecular Chemistry Royal Society of Chemistry 16 (4) 541 - 544 1477-0520 2018 [Refereed]
   

  A mild oxidation method for the conversion of aldoximes to carboxylic acids was developed mediated by hypervalent iodine reagents. This method covers a wide range of functionalized aldoximes and proceeds under mild conditions, utilizing PhI(OH)OTs as an oxidant.
• Catalyst-Dependent Selective Hydrogenation of Nitriles: Selective Synthesis of Tertiary and Secondary Amines

  Yasunari Monguchi; Masahiro Mizuno; Tomohiro Ichikawa; Yuki Fujita; Eri Murakami; Tomohiro Hattori; Tomohiro Maegawa; Yoshinari Sawama; Hironao Sajiki

  JOURNAL OF ORGANIC CHEMISTRY AMER CHEMICAL SOC 82 (20) 10939 - 10944 0022-3263 2017/10 [Refereed]
   

  In the presence of palladium on carbon (Pd/C) as a catalyst, hydrogenation of aliphatic nitriles in cyclohexane efficiently proceeded at 25-60 degrees C under ordinary hydrogen gas pressure to afford the corresponding tertiary amines. However, the use of rhodium on carbon (Rh/C) led to the highly selective generation of secondary amines. Hydrogenation of aromatic nitriles and cyclohexanecarbonitrile selectively produced secondary amines in the presence of either Pd/C or Rh/C.
• Versatile and chemoselective synthesis of fluorinated methyl ethers from methoxymethyl ethers

  Reiya Ohta; Yuichi Kuboki; Yuki Yoshikawa; Yasuyuki Koutani; Tomohiro Maegawa; Hiromichi Fujioka

  JOURNAL OF FLUORINE CHEMISTRY ELSEVIER SCIENCE SA 201 1 - 6 0022-1139 2017/09 [Refereed]
   

  A versatile and chemoselective route has been developed for the synthesis of aliphatic fluorinated methyl ethers (ROCH2RF), specifically monofluoromethyl ethers (ROCH2F) and trifluoromethylthiomethyl ethers (ROCH2SCF3), through pyridinium-type salt intermediates derived from methoxymethyl (MOM) ethers. The addition of a fluorine source (F- or SCF3-) to the pyridinium-type salts afforded the corresponding fluorinated methyl ethers in good yields under mild conditions. Notably, the synthesis of monofluoromethyl ethers proceeded within just 5 min.
• Synthesis of 3-acylindoles by oxidative rearrangement of 2-aminochalcones using a hypervalent iodine reagent and cyclization sequence

  Akira Nakamura; Satoshi Tanaka; Akira Imamiya; Reo Takane; Chiaki Ohta; Kazuma Fujimura; Tomohiro Maegawa; Yasuyoshi Miki

  ORGANIC & BIOMOLECULAR CHEMISTRY ROYAL SOC CHEMISTRY 15 (32) 6702 - 6705 1477-0520 2017/08 [Refereed]
   

  An efficient one-pot method was developed for the construction of 3-acylindoles via oxidative rearrangement of 2-aminochalcones followed by intramolecular cyclization. The reaction was used to convert a variety of 2-aminochalcones into 3-acylindoles in moderate to high yields.
• Transformation of Methylene Acetals to Bromoformates with a Combination of Trimethyl(phenylthio)silane and N-Bromosuccinimide

  Tomohiro Maegawa; Misa Nogata; Yuuka Hirose; Shun Ohgami; Akira Nakamura; Yasuyoshi Miki; Hiromichi Fujioka

  Journal of Organic Chemistry American Chemical Society 82 (14) 7608 - 7613 1520-6904 2017/07 [Refereed]
   

  A novel transformation reaction of methylene acetals, using a combination of trimethyl(phenylthio)silane (PhSTMS) and N-bromosuccinimide (NBS) under mild reaction conditions, is described. Various methylene acetals were converted to their corresponding bromoformates in good to high yields. Under the given conditions, the reaction proceeded via a radical pathway. Further transformation of bromoformates to their corresponding epoxides was achieved by treatment with NaOMe.
• HALOGENATION OF DIMETHYL INDOLE-2,3-DICARBOXYLATES USING PhI(OAc)(2) AND ALKALI METAL HALIDE

  Yasuyoshi Miki; Yukari Hirata; Noriko Makino; Yuuka Hirose; Misa Nogata; Akira Nakamura; Hiromi Hamamoto; Tomohiro Maegawa

  HETEROCYCLES PERGAMON-ELSEVIER SCIENCE LTD 94 (7) 1269 - 1279 0385-5414 2017/07 [Refereed]
   

  We studied selective bromination and iodination of dimethyl indole-2,3-dicarboxylates using phenyliodine diacetate (PIDA), LiBr, and LiI in the presence of Lewis acid. The protective group on the nitrogen of indole is important for selectivity of the halogenation position, and the use of a benzenesulfonyl group as a protective group resulted in preferential halogenation of indole at the 6-position.
• 2-ARYLQUINOLINE SYNTHESIS FROM Cbz-PROTECTED 2-AMINO-CHALCONE MEDIATED BY BF3 center dot Et2O

  Tomohiro Maegawa; Misa Nogata; Takaya Honda; Akira Nakamura; Yasuyoshi Miki

  HETEROCYCLES PERGAMON-ELSEVIER SCIENCE LTD 95 (1) 608 - 614 0385-5414 2017/01 [Refereed][Invited]
   

  A novel approach to producing the quinoline skeleton from 2-aminochalcone was developed. Treatment of benzyloxycarbonyl (Cbz)-protected 2-aminochalcones with BF3 center dot Et2O afforded quinoline derivatives via the deprotection of the Cbz group and isomerization of olefin in a one-pot reaction. The reaction of various 2-aminochalcones proceeded to give the corresponding 2-arylquinoline derivatives in good yields. This method is applicable to the rapid synthesis of dubamine.
• DECARBOXYLATIVE HALOGENATION OF INDOLECARBOXYLIC ACIDS USING HYPERVALENT IODINE(III) REAGENT AND ITS APPLICATION TO THE SYNTHESIS OF POLYBROMOINDOLES

  Hiromi Hamamoto; Hideaki Umemoto; Misako Umemoto; Chiaki Ohta; Emi Fujita; Akira Nakamura; Tomohiro Maegawa; Yasuyoshi Miki

  HETEROCYCLES PERGAMON-ELSEVIER SCIENCE LTD 91 (3) 561 - 572 0385-5414 2015/03 [Refereed]
   

  Hypervalent iodine mediated decarboxylative halogenation of indoledicarboxylic acid derivatives was studied. The treatment of 1-methylindole-2,3-dicarboxylic acid with phenyliodine diacetate (PIDA) in the presence of lithium bromide gave 1-methyl-3,3-bromooxindole. However, the reaction of 1-(phenylsulfonyl)indole-2,3-dicarboxylic acid with PIDA in the presence of lithium bromide afforded 2,3-dibromo-1-(phenylsulfonyl)indole. In a similar manner, the 2,3-dichloro- and 2,3-diiodoindole derivatives could be obtained by the reaction of the indole-2,3-dicarboxylic acids with PIDA in the presence of lithium chloride and iodide. This method was optimized to the synthesis of polybromoindole alkaloids.
• Reactions of 2-[Lithio(trimethylsilyl)methyl]-2H-tetrazoles: Synthesis of 2-[1-(Trimethylsilyl) alkyl]-2H-tetrazoles and (2H-Tetrazol-2-yl) acetates

  Hideaki Umemoto; Takuya Onaka; Yasuyoshi Miki; Akira Nakamura; Tomohiro Maegawa

  SYNLETT GEORG THIEME VERLAG KG 26 (2) 205 - 208 0936-5214 2015/01 [Refereed]
   

  The reaction of 2-[(trimethylsilyl) methyl]-2H-tetrazoles with various alkyl halides and carbonates using n-butyllithium or lithium diisopropylamide (LDA) gave 2-[1-(trimethylsilyl) alkyl]-2H-tetrazoles and (2H-tetrazol-2-yl) acetates as useful synthons of modified tetrazoles.
• THE REACTION OF 2-((TRIMETHYLSILYL)METHYL)-2H-TETRAZOLES WITH ALDEHYDES AND KETONES IN THE PRESENCE OF 1,8-DIAZABICYCLO [5.4.0]UNDEC-7-ENE

  Hideaki Umemoto; Takuya Onaka; Yasuyoshi Miki; Akira Nakamura; Tomohiro Maegawa

  HETEROCYCLES PERGAMON-ELSEVIER SCIENCE LTD 89 (11) 2545 - 2553 0385-5414 2014/11 [Refereed]
   

  2-((Trimethylsilyl)methyl)-2H-tetrazoles were treated with aldehydes and ketones in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) to give 2-(2-hydroxyethyl)-2H-tetrazoles. This simple procedure offers a valuable strategy for the preparation of 2-(hydroxyethyl)-2H-tetrazoles.
• [Cu(OH)(TMEDA)](2)Cl-2-Catalyzed Regioselective 2-Arylation of 5-Substituted Tetrazoles with Boronic Acids under Mild Conditions

  Takuya Onaka; Hideaki Umemoto; Yasuyoshi Miki; Akira Nakamura; Tomohiro Maegawa

  JOURNAL OF ORGANIC CHEMISTRY AMER CHEMICAL SOC 79 (14) 6703 - 6707 0022-3263 2014/07 [Refereed]
   

  A mild and regioselective 2-arylation of 5-substituted tetrazoles is described. The reaction proceeds regioselectively with a variety of arylboronic acids in the presence of [Cu(OH)(TMEDA)](2)Cl-2 to afford 2,5-disubstituted tetrazoles. This is the first report of highly regioselective arylation of 5-alkyltetrazoles.
• Cu/HP20-CATALYZED SOLVENT-FREE HUISGEN CYCLOADDITION AT ORDINARY TEMPERATURES

  Yoshiaki Kitamura; Kazumi Taniguchi; Tomohiro Maegawa; Yasunari Monguchi; Yukio Kitade; Hironao Sajiki

  HETEROCYCLES PERGAMON-ELSEVIER SCIENCE LTD 88 (1) 233 - 243 0385-5414 2014/01 [Refereed]
   

  We have developed an environmentally friendly and highly efficient solvent-free Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC) reaction using a polymer-supported copper catalyst (Cu/HP20). Substrates poorly soluble in common organic solvents are also applicable to the present cycloaddition reaction without any solvents and provide the corresponding 1,4-triazole in high yields.
• Reaction via Pyridinium-type Salt Intermediate: Chemoselective DeProtection of Acetals in the Presence of Ketals and Nucleophilic Substitution

  Tomohiro Maegawa; Hiromichi Fujioka

  JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY JAPAN SOC SYNTHETIC ORGANIC CHEM JPN 71 (7) 694 - 705 0037-9980 2013/07 [Refereed]
   

  Although acetals are useful protective groups for carbonyl functions and widely used in organic synthesis, their protection and deprotection under acidic conditions unable to use the substrates with acid labile functions. We recently found that the combination of TESOTf (Et3Si0Tf) 2,6lutidine or 2,4,6-collidine was effective for the deprotection of acetal. The reaction proceeded under nearly neutral conditions and was applicable to the substrates with acid labile functions, and the most noteworthy of this method is the achievement of the chemoselective deprotection of acetals in the presence of ketals. The above reaction proceeds via pyridinium-type salt intermediates, which are found to be highly reactive toward various nucleophiles not only H20 but also heteroatom and carbon nucleophiles affording the corresponding substituted products. This reaction could be conducted under mild reaction conditions whereas conventional methods need harsh reaction conditions. This methodology is also applicable to the deprotection of acetal-type protective groups such as MOM-type ethers, THP ether, and methylene acetal, and the combination of TMSOTf (TESOTf) 2,2'-bipyridyl afforded the best result
• Methylene acetal formation from 1,2- and 1,3-diols using an O, S -acetal, 1,3-dibromo-5,5-dimethylhydantoin, and BHT

  Tomohiro Maegawa; Yasuyuki Koutani; Kazuki Otake; Hiromichi Fujioka

  Journal of Organic Chemistry 78 (7) 3384 - 3390 0022-3263 2013/04 [Refereed]
   

  A mild and efficient method for formation of methylene acetals from 1,2- and 1,3-diols using methoxymethylphenylsulfide, 1,3-dibromo-5,5- dimethylhydantoin (DBDMH), and dibutylhydroxytoluene (BHT) is described. The use of BHT in this process suppresses side reactions and enables high-yielding formation of methylene acetals of various diols, including carbohydrate-type substrates. © 2013 American Chemical Society.
• Friedel-Crafts/Protonation反応およびFriedel-Crafts/Henry反応 Gilman試薬 ホスファゼン塩基 ホスホロアミダイト

  荒井 孝義; 前川 智弘; 藤岡 弘道; 佐藤 敏文; 山本 靖典

  有機合成化学協会誌 The Society of Synthetic Organic Chemistry, Japan 71 (7) 731 - 731 0037-9980 2013
• Chemoselective hydrogenation using molecular sieves-supported Pd catalysts: Pd/MS3A and Pd/MS5A

  Takahashi Tohru; Yoshimura Masatoshi; Suzuka Hiroyasu; Maegawa Tomohiro; Sawama Yoshinari; Monguchi Yasunari; Sajiki Hironao

  TETRAHEDRON 68 (39) 8293 - 8299 0040-4020 2012/09 [Refereed]
  
• Effects of Phosphorus Substituents on Reactions of alpha-Alkoxyphosphonium Salts with Nucleophiles

  Akihiro Goto; Kazuki Otake; Ozora Kubo; Yoshinari Sawama; Tomohiro Maegawa; Hiromichi Fujioka

  CHEMISTRY-A EUROPEAN JOURNAL WILEY-V C H VERLAG GMBH 18 (36) 11423 - 11432 0947-6539 2012/09 [Refereed]
   

  The effects of phosphorus substituents on the reactivity of alpha-alkoxyphosphonium salts with nucleophiles has been explored. Reactions of a-alkoxyphosphonium salts, prepared from various acetals and tri(o-tolyl)-phosphine, with a variety of nucleophiles proceeded efficiently. These processes represent the first examples of high-yielding nucleophilic substitution reactions of a-alkoxyphosphonium salts. The reactivity of these salts was determined by a balance between steric and electronic factors, respectively, represented by cone angles theta and CO stretching frequencies nu (steric and electronic parameters, respectively). In addition, a novel reaction of a-alkoxyphosphonium salts derived from Ph3P with Grignard reagents was observed to take place in the presence of O-2 to afford alcohols in good yields. A radical mechanism is proposed for this process that has gained support from isotope-labeling and radical-inhibition experiments.
• Method for the Efficient Synthesis of Highly-Substituted Oxetan- and Azetidin-, Dihydrofuran- and Pyrrolidin-3-ones and Its Application to the Synthesis of (+/-)Pseudodeflectusin

  Tomohiro Maegawa; Kazuki Otake; Keiichi Hirosawa; Akihiro Goto; Hiromichi Fujioka

  ORGANIC LETTERS AMER CHEMICAL SOC 14 (18) 4798 - 4801 1523-7060 2012/09 [Refereed]
   

  Highly substituted four- and five-membered heterocycles were prepared starting with O,P- and N,P-acetals by using a one-pot method involving base induced cyclization and a Horner-Wadsworth-Emmons (HWE) olefination reaction. Divergent synthesis of various heterocycles was achieved by using this method and transformations of the alkenyl group in the products of these processes were exemplified. Finally, a short and efficient synthesis of (+/-)-pseudodeflectusin based on the new methodology was achieved.
• A Mild and Versatile Method for the Synthesis of Alkyl Ethers from Methoxymethyl Ethers and Application to the Preparation of Sterically Crowded Ethers

  Yutaka Minamitsuji; Atsuhisa Kawaguchi; Ozora Kubo; Yoshifumi Ueyama; Tomohiro Maegawa; Hiromichi Fujioka

  ADVANCED SYNTHESIS & CATALYSIS WILEY-V C H VERLAG GMBH 354 (10) 1861 - 1866 1615-4150 2012/07 [Refereed]
   

  A mild and divergent route for the synthesis of alkyl ethers from methoxymethyl (MOM) and methoxyethyl (ME) ether derivatives via pyridinium-type salt intermediates has been developed. The addition of organocuprates to the salts afforded the corresponding alkyl ethers, including highly crowded ones, in high yields even in the presence of acid- or base-sensitive functional groups.
• Platinum on Carbon-Catalyzed Hydrodefluorination of Fluoroarenes using Isopropyl Alcohol-Water-Sodium Carbonate Combination

  Sawama Yoshinari; Yabe Yuki; Shigetsura Masahiro; Yamada Tsuyoshi; Nagata Saori; Fujiwara Yuta; Maegawa Tomohiro; Monguchi Yasunari; Sajiki Hironao

  ADVANCED SYNTHESIS & CATALYSIS Wiley 354 (5) 777 - 782 1615-4150 2012/03 [Refereed]
  
• Reaction of Acetals with Various Carbon Nucleophiles under Non-Acidic Conditions: C-C Bond Formation via a Pyridinium-Type Salt

  Hiromichi Fujioka; Kenzo Yahata; Tomohito Hamada; Ozora Kubo; Takashi Okitsu; Yoshinari Sawama; Takuya Ohnaka; Tomohiro Maegawa; Yasuyuki Kita

  CHEMISTRY-AN ASIAN JOURNAL WILEY-V C H VERLAG GMBH 7 (2) 367 - 373 1861-4728 2012/02 [Refereed]
   

  Mild substitution reactions of acetals with carbon nucleophiles via the pyridinium-type salts generated by the treatment of acetals with TESOTf-2,4,6-collidine or 2,2'-bipyridyl have been developed. Various carbon nucleophiles, such as organocuprates, silyl enol ethers, enamines, etc., reacted with the pyridinium-type salts to give the corresponding substituted products in good yields. The reactions proceeded under very mild conditions (non-acidic conditions) and thus acid-sensitive functional groups can be tolerated during the reaction. In addition, only an acetal can form the pyridinium-type salt and react with nucleophiles in the presence of a ketal. This unusual selectivity is in contrast to general methods conducted under acidic conditions.
• DEUTERIUM-LABELED BENZYLADENINE: SYNTHESIS AND APPLICATION AS A SURROGATE

  Nkaelang Modutlwa; Hiroyuki Tada; Yoshiki Sugahara; Koichi Shiraki; Nobuyuki Hara; Yoshihiro Deyashiki; Tomohiro Maegawa; Yasunari Monguchi; Hironao Sajiki

  HETEROCYCLES PERGAMON-ELSEVIER SCIENCE LTD 84 (1) 419 - 429 0385-5414 2012/01 [Refereed]
   

  N-6-Benzyladenine (benzyladenine), a plant growth regulator, was efficiently deuterated by the hydrogen deuterium (H D) exchange reaction catalyzed by palladium on carbon-ethylenediamine complex [Pd/C(en)], while use of palladium on carbon (Pd/C) as a catalyst led to a low deuterium incorporation at room temperature or complete removal of the N-6-benzyl group at 110 degrees C or higher temperature. The obtained benzyladenine-d(5) was used as an internal standard (surrogate) for the quantification of residual benzyladenine in fruits, vegetables, cereals, and beans using LC/MS/MS. Satisfactory recovery of benzyladenine between 94.2 and 105.7% (100.4% on the average) was obtained. The agrochemical could be detected within the concentration range of 0.25-0.50 ng/g in agricultural products using the present quantification method.
• Selective deprotection of methylene acetal and mom ether in the presence of ketal-type protective groups: Remarkable effect of tbsot

  Maegawa T; Koutani Y; Senami K; Yahata K; Fujioka H

  Heterocycles 86 (1) 455 - 467 2012 [Refereed]
  
• Selective N-alkylation of amines using nitriles under hydrogenation conditions: facile synthesis of secondary and tertiary amines

  Takashi Ikawa; Yuki Fujita; Tomoteru Mizusaki; Sae Betsuin; Haruki Takamatsu; Tomohiro Maegawa; Yasunari Monguchi; Hironao Sajiki

  ORGANIC & BIOMOLECULAR CHEMISTRY ROYAL SOC CHEMISTRY 10 (2) 293 - 304 1477-0520 2012 [Refereed]
   

  Nitriles were found to be highly effective alkylating reagents for the selective N-alkylation of amines under catalytic hydrogenation conditions. For the aromatic primary amines, the corresponding secondary amines were selectively obtained under Pd/C-catalyzed hydrogenation conditions. Although the use of electron poor aromatic amines or bulky nitriles showed a lower reactivity toward the reductive alkylation, the addition of NH4OAc enhanced the reactivity to give secondary aromatic amines in good to excellent yields. Under the same reaction conditions, aromatic nitro compounds instead of the aromatic primary amines could be directly transformed into secondary amines via a domino reaction involving the one-pot hydrogenation of the nitro group and the reductive alkylation of the amines. While aliphatic amines were effectively converted to the corresponding tertiary amines under Pd/C-catalyzed conditions, Rh/C was a highly effective catalyst for the N-monoalkylation of aliphatic primary amines without over-alkylation to the tertiary amines. Furthermore, the combination of the Rh/C-catalyzed N-monoalkylation of the aliphatic primary amines and additional Pd/C-catalyzed alkylation of the resulting secondary aliphatic amines could selectively prepare aliphatic tertiary amines possessing three different alkyl groups. According to the mechanistic studies, it seems reasonable to conclude that nitriles were reduced to aldimines before the nucleophilic attack of the amine during the first step of the reaction.
• (+)-Sorangicin A: evolution of a viable synthetic strategy

  Amos B. Smith; Shuzhi Dong; Richard J. Fox; Jehrod B. Brenneman; John A. Vanecko; Tomohiro Maegawa

  TETRAHEDRON PERGAMON-ELSEVIER SCIENCE LTD 67 (51) 9809 - 9828 0040-4020 2011/12 [Refereed]
   

  An effective, asymmetric total synthesis of the antibiotic (+)-sorangicin A (1) has been achieved. Central to this venture was the development of first- and second-generation syntheses of the signature dioxabicyclo[3.2.1]octane core, the first featuring chemo- and stereoselective epoxide ring openings facilitated by a Co-2(Co)(6)-alkyne complex, the second involving a KHMDS-promoted epoxide ring formation/opening cascade. Additional highlights include effective construction of the dihydro- and tetrahydropyran ring systems, respectively, via a stereoselective conjugate addition/alpha-oxygenation protocol and a thioketalization/hydrostannane reduction sequence. Late-stage achievements entailed two Julia-Kocienski olefinations to unite three advanced fragments with high E-stereoselectivity, followed by a modified Stille protocol to introduce the Z,Z,E trienoate moiety, thereby completing the carbon skeleton. Mukaiyama macrolactonization, followed by carefully orchestrated Lewis and protic acid-promoted deprotections that suppressed isomerization and/or destruction of the sensitive (Z,Z,E)-trienoate linkage completed the first, and to date only, total synthesis of (+)-sorangicin A (1). (C) 2011 Elsevier Ltd. All rights reserved.
• Palladium on carbon-catalyzed solvent-free and solid-phase hydrogenation and Suzuki-Miyaura reaction

  Yasunari Monguchi; Yuki Fujita; Shota Hashimoto; Mariko Ina; Tohru Takahashi; Ryo Ito; Kei Nozaki; Tomohiro Maegawa; Hironao Sajiki

  TETRAHEDRON PERGAMON-ELSEVIER SCIENCE LTD 67 (45) 8628 - 8634 0040-4020 2011/11 [Refereed]
   

  The solvent-free and solid-phase hydrogenation of various reducible functionalities was efficiently catalyzed by heterogeneous palladium on carbon (Pd/C) under ambient hydrogen pressure and temperature. The Pd/C-catalyzed Suzuki-Miyaura coupling reaction between solid aryl bromides and solid arylboronic acids to generate the corresponding solid biaryls was also achieved under the totally solid-phase conditions. (C) 2011 Elsevier Ltd. All rights reserved.
• Facile Hydrogenation of Ketones Catalyzed by Platinum on Carbon under Ordinary Pressures and Temperatures

  Yuta Fujiwara; Youhei Iwasaki; Tomohiro Maegawa; Yasunari Monguchi; Hironao Sajiki

  CHEMCATCHEM WILEY-BLACKWELL 3 (10) 1624 - 1628 1867-3880 2011/10 [Refereed]
   

  An efficient and practical procedure for the hydrogenation of aliphatic and aromatic ketones under mild reaction conditions is established. The method is highly effective even for the hydrogenation of sterically hindered ketones. Furthermore, the selective hydrogenation of the carbonyl group of aromatic ketones was achieved with the aromatic nuclei and the resulting secondary benzyl alcohol moiety still intact on addition of catalytic amount of pyridine.
• Direct conversion of acetals to esters with high regioselectivity via O,P-acetals

  Tomohiro Maegawa; Kazuki Otake; Akihiro Goto; Hiromichi Fujioka

  ORGANIC & BIOMOLECULAR CHEMISTRY ROYAL SOC CHEMISTRY 9 (16) 5648 - 5651 1477-0520 2011 [Refereed]
   

  A new direct conversion of O,O-acetals to esters via O,P-acetal intermediates was developed. The regioselective cleavage of unsymmetrical cyclic acetals occurred to give the more crowded esters as single isomers.
• 2,5-cis-2,3,5-Trisubstituted tetrahydrofurans from the diastereomixture of 2,4-disubstituted 1,3-dioxepins via stereomutation

  Ozora Kubo; Kenzo Yahata; Tomohiro Maegawa; Hiromichi Fujioka

  CHEMICAL COMMUNICATIONS ROYAL SOC CHEMISTRY 47 (32) 9197 - 9199 1359-7345 2011 [Refereed]
   

  A diastereoselective ring contraction of the diastereomixture of 2,4-disubstituted 1,3-dioxepins to 2,5-cis-2,3,5-trisubstituted tetrahydrofurans was achieved using TfOH in DMF. The reaction appears to proceed via a chair-like transition state, in which stereomutation of the oxocarbenium occurred, followed by an aldol-type cyclization.
• An unusual reaction of alpha-alkoxyphosphonium salts with Grignard reagents under an O-2 atmosphere

  Hiromichi Fujioka; Akihiro Goto; Kazuki Otake; Ozora Kubo; Yoshinari Sawama; Tomohiro Maegawa

  CHEMICAL COMMUNICATIONS ROYAL SOC CHEMISTRY 47 (35) 9894 - 9896 1359-7345 2011 [Refereed]
   

  An unusual and novel reaction of alpha-alkoxyphosphonium salts, generated from O,O-acetals and Ph3P, with Grignard reagents under an O-2 atmosphere afforded alcohols in moderate to high yields. It was clarified by isotopic labelling experiments that the reaction proceeded via a novel radical pathway.
• Reversing the Reactivity of Carbonyl Functions with Phosphonium Salts: Enantioselective Total Synthesis of (+)-Centrolobine

  Hiromichi Fujioka; Kenzo Yahata; Ozora Kubo; Yoshinari Sawama; Tomohito Hamada; Tomohiro Maegawa

  ANGEWANDTE CHEMIE-INTERNATIONAL EDITION WILEY-V C H VERLAG GMBH 50 (51) 12232 - 12235 1433-7851 2011 [Refereed]
  
• Pd/C-catalyzed a-oxygenation of 1,3-dicarbonyl compounds using molecular oxygen

  Tohru Takahashi; Yusuke Iida; Yuta Fujiwara; Yuya Inagaki; Tomohiro Maegawa; Yasunari Monguchi; Hironao Sajiki

  ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY AMER CHEMICAL SOC 239 0065-7727 2010/03
• Hetero-Suzuki-Miyaura Cross-Coupling Using Palladium on Carbon

  Kitamura Yoshiaki; Sako Satoko; Tsutsui Azusa; Monguchi Yasunari; Maegawa Tomohiro; Kitade Yukio; Sajiki Hironao

  Synfacts GEORG THIEME VERLAG KG 7 844 - 844 2010
• LC-MS/MSを用いたクロバザムとその代謝物であるN-デスメチルクロバザムの高速及び高感度なハイスループット分析

  谷口 和美; 中村 光浩; 大森 智史; 門口 泰也; 前川 智弘; 井口 和弘; 伊藤 善規; 臼井 茂之; 佐治木 弘尚; 平野 和行

  日本薬学会年会要旨集 (公社)日本薬学会 129年会 (4) 100 - 100 0918-9823 2009/03
• ORGN 537-Practical method for PCBs degradation using Pd/C-H2-Mg system

  Akiko Ido; Shinji Ishihara; Ryota Kobayashi; Akira Kume; Tomohiro Maegawa; Yasunari Monguchi; Sueo Wada; Hironao Sajiki; Hisamitsu Nagase

  ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY AMER CHEMICAL SOC 237 0065-7727 2009/03 [Refereed]
  
• ORGN 270-Facile Pd/C-catalyzed degradation of environmentally hazardous chlorinated organic compounds

  Yasunari Monguchi; Akira Kume; Shinji Ishihara; Sueo Wada; Tomohiro Maegawa; Hisamitsu Nagase; Hironao Sajiki

  ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY AMER CHEMICAL SOC 237 0065-7727 2009/03 [Refereed]
  
• ORGN 572-Hydrogen gas-free Pd/C-catalyzed PCB degradation

  Shinji Ishihara; Akiko Ido; Tomohiro Maegawa; Yasunari Monguchi; Sueo Wada; Hisamitsu Nagase; Hironao Sajiki

  ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY AMER CHEMICAL SOC 237 0065-7727 2009/03 [Refereed]
  
• Synthesis of deuterated benzyladenine and its application as a surrogate.

  Nkaelang Modutlwa; Hiroyuki Tada; Yoshiki Sugahara; Koichi Shiraki; Nobuyuki Hara; Yoshihiro Deyashiki; Takayuki Ando; Tomohiro Maegawa; Yasunari Monguchi; Hironao Sajiki

  Nucleic acids symposium series (2004) (53) 105 - 106 2009 [Refereed]
   

  Palladium on carbon-ethylenediamine complex [Pd/C(en)] catalyzed deuteration of N(6)-benzyladenine-d(5), which is a plant growth regulator, to introduce 5 deuterium atoms, while use of Pd/C as a catalyst led to a complete removal of N(6)-benzyl group. The corresponding deuterated N(6)-benzyladenine was successfully used as a surrogate compound for the quantitative analysis of residual benzyladenine in crops using LC/MS/MS.
• Novel palladium-on-carbon/diphenyl sulfide complex for chemoselective hydrogenation: Preparation, characterization, and application

  Akinori Mori; Tomoteru Mizusaki; Masami Kawase; Tomohiro Maegawa; Yasunari Monguchi; Shinobu Takao; Yukio Takagi; Hironao Sajiki

  ADVANCED SYNTHESIS & CATALYSIS WILEY-BLACKWELL 350 (3) 406 - 410 1615-4150 2008/02 [Refereed]
   

  A diphenyl sulfide immobilized on palladium-on-carbon system, Pd/C[Ph(2)S], was developed to achieve the highly chemoselective hydrogenation of alkenes, acetylenes, azides, and nitro groups in the presence of aromatic ketones, halides, benzyl esters, and N-Cbz protective groups. Instrumental analyses of the heterogeneous catalyst demonstrated that diphenyl sulfide was embedded on Pd/C via coordination of its sulfur atom to palladium metal or physical interaction with graphite layers of the activated carbon. The catalyst could be recovered and reused at least five times without any significant loss of the reactivity.
• Efficient and selective Pt/C-catalyzed H-D exchange reaction of aromatic rings

  Nobuhiro Ito; Hiroyoshi Esaki; Tsuneaki Maesawa; Eikoh Imamiya; Tomohiro Maegawa; Hironao Sajiki

  BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN CHEMICAL SOC JAPAN 81 (2) 278 - 286 0009-2673 2008/02 [Refereed]
   

  An effective and applicable deuteration method for aromatic rings using Pt/C-D2O-H-2 system was established. Especially, phenol was fully deuterated even at room temperature, and other electron-rich aromatic nuclei were efficiently deuterated under mild conditions. The scope and limitations of the presence method and its application to the synthesis of deuterium-labeled biologically active compounds and deuterium-labeled building blocks for practical multi-gram scale syntheses are reported.
• 不均一系パラジウム触媒を用いた効率的鈴木－宮浦反応の開発

  Monguchi Yasunari(Gifu; Pharmaceutical University; Kitamura Yoshiaki(Gifu University; Maegawa Tomohiro(Gifu; Pharmaceutical University; Sajiki Hironao(Gifu; Pharmaceutical University

  ケミカルエンジニアリング 化学工業社 53 (4) 256 - 261 0387-1037 2008
• Ligand-free Sonogashira coupling reactions with heterogeneous Pd/C as the catalyst.

  Mori S; Yanase T; Aoyagi S; Monguchi Y; Maegawa T; Sajiki H

  Chemistry (Weinheim an der Bergstrasse, Germany) 14 (23) 6994 - 6999 0947-6539 2008 [Refereed]
   

  A variety of aryl iodides were coupled with aromatic and aliphatic terminal alkynes to give the corresponding 1,2-disubstituted aromatic alkynes in good yields by using only 0.4 mol % of the heterogeneous 10 % Pd/C as the catalyst without a ligand, copper salt, or amine in an aqueous medium.
• Ligand-free Pd/C-catalyzed Suzuki-Miyaura coupling reaction for the synthesis of heterobiaryl derivatives

  Yoshiaki Kitamura; Satoko Sako; Takahiro Udzu; Azusa Tsutsui; Tomohiro Maegawa; Yasunari Monguchi; Hironao Sajiki

  Chemical Communications ROYAL SOC CHEMISTRY 5069 - 5071 1359-7345 2007/12 [Refereed]
   

  We have developed a mild and efficient protocol for the ligand-free and heterogeneous Pd/C-catalyzed hetero Suzuki-Miyaura coupling reaction that allows for the synthesis of both heteroaryl-aryl and heteroaryl-heteroaryl derivatives in good to excellent yields. © The Royal Society of Chemistry.
• Ligand- and base-free synthesis of 1,3-diynes catalyzed by low loading of heterogeneous Pd/C and cuI

  Takanori Kurita; Masami Abe; Tomohiro Maegawa; Yasunari Monguchi; Hironao Sajiki

  SYNLETT GEORG THIEME VERLAG KG (16) 2521 - 2524 0936-5214 2007/10 [Refereed]
   

  A facile and environmentally friendly synthetic method for a variety of symmetrical 1,3-diyne derivatives based on the Pd/C-Cul-catalyzed homocoupling reaction of terminal alkynes has been developed. The reaction was efficiently catalyzed by the extrernely low loading (0.01-0.03 mol%) of Pd/C and Cul (3 mol%) in the presence of molecular oxygen (02) as an oxidant without any phosphine ligands and bases.
• Heterogeneous Pd/C-catalyzed ligand-free Suzuki-Miyaura coupling reaction using aryl boronic esters

  Yoshiaki Kitamura; Ai Sakurai; Takahiro Udzu; Tomohiro Maegawa; Yasunari Monguchi; Hironao Sajiki

  Tetrahedron PERGAMON-ELSEVIER SCIENCE LTD 63 (43) 10596 - 10602 0040-4020 2007/10 [Refereed]
   

  Heterogeneous Pd/C-catalyzed Suzuki-Miyaura cross-coupling reaction of aryl boronic esters with aryl bromides was successfully carried out in aqueous media at room temperature without the use of a ligand such as phosphine derivatives. © 2007 Elsevier Ltd. All rights reserved.
• Heterogeneous Pd/C-catalyzed ligand-free, room-temperature suzuki-miyaura coupling reactions in aqueous media

  Tomohiro Maegawa; Yoshiaki Kitamura; Satoko Sako; Takahiro Udzu; Ai Sakurai; Asami Tanaka; Yusuke Kobayashi; Koichi Endo; Utpal Bora; Takanori Kurita; Atsushi Kozaki; Yasunari Monguchi; Hironao Sajiki

  Chemistry - A European Journal WILEY-V C H VERLAG GMBH 13 (20) 5937 - 5943 0947-6539 2007/08 [Refereed]
   

  A mild and efficient ligand-free Suzuki-Miyaura coupling reaction catalyzed by heterogeneous Pd/C was developed. Aryl bromides and triflates undergo the cross-coupling with aryl boronic acids in excellent yields without the presence of any additives in aqueous media at room temperature. Aryl vinyl boronic acids are also applicable to this coupling reaction and provide the trans-stilbene derivatives in high yields. The application of wet-type Pd/C to the coupling reaction was achieved without any loss of activity under aerobic conditions, and the reuse of Pd/C is feasible for a fifth run without significant loss of activity. Inductively coupled plasma (ICP) mass-spectrometric analysis of the filtrate from the reaction mixture of 4-bromonitrobenzene with phenylboronic acid demonstrated that the palladium metal hardly leached into the solution within the limits of the detector (< 1 ppm), thus suggesting that the present Suzuki-Miyaura reaction proceeded by heterogeneous catalysis. © 2007 Wiley-VCH Verlag GmbH & Co. KGaA.
• Pd/C(en) catalyzed chemoselective hydrogenation in the presence of aryl nitriles

  Tomohiro Maegawa; Yuki Fujita; Ai Sakurai; Akira Akashi; Mutsumi Sato; Keiji Oono; Hironao Sajiki

  CHEMICAL & PHARMACEUTICAL BULLETIN PHARMACEUTICAL SOC JAPAN 55 (5) 837 - 839 0009-2363 2007/05 [Refereed]
   

  Aromatic nitriles are not only important components of natural products, pharmaceuticals, herbicides and agrochemicals but also a synthetic equivalent of various functionalities. The development of synthetic methods of aromatic nitriles have been increasing in terms of its usefulness. Since aromatic nitriles are susceptible to the hydrogenation, it has been desired for the development of chemoselective hydrogenation method with retention of nitrile groups. Pd/C is one of the most popular catalysts for hydrogenation and many of reducible functional groups such as multiple bonds, benzyl ethers, N-Cbzs, nitro groups and so on could be easily reduced under the conditions. Therefore, it is very difficult to achieve the chemoselective hydrogenation of substrates containing two or more reducible functional groups. We have found that a Pd/C catalyst formed an isolable complex with ethylenediamine (en) employed as catalytic poison, and the complex [Pd/C(en)] catalyzed chemoselective hydrogenation of a variety of reducible functionalities distinguishing O-benzyl, N-Cbz and O-TBDMS protective groups, benzyl alcohols and epoxides. In the course of these investigations, we found the aryl nitriles could survive under the Pd/C(en)-catalyzed hydrogenation conditions in THF whose choice is important for the effective suppression. This methodology could be applied to the selective hydrogenation of alkene and alkyne functionalities in the presence of aromatic nitrile.
• Novel Pd/C-catalyzed redox reactions between aliphatic secondary alcohols and ketones under hydrogenation conditions: Application to H-D exchange reaction and the mechanistic study

  Hiroyoshi Esaki; Rumi Ohtaki; Tomohiro Maegawa; Yasunari Monguchi; Hironao Sajiki

  JOURNAL OF ORGANIC CHEMISTRY AMER CHEMICAL SOC 72 (6) 2143 - 2150 0022-3263 2007/03 [Refereed]
   

  A liquid-phase redox system between secondary alcohols and ketones is described. Deuteration of either secondary alcohols or ketones using the Pd/C-H-2-D2O system gave a mixture of deuterium-labeled secondary alcohols and ketones. The results indicated that the secondary alcohol was oxidized to the corresponding ketone without oxidants under the hydrogenation conditions and the hydrogenation of the aliphatic ketone to the corresponding secondary alcohol simultaneously proceeded. Detailed mechanistic studies on the redox system as well as the H-D exchange reaction are discussed.
• Palladium on carbon-diethylamine-mediated hydrodeoxygenation of phenol derivatives under mild conditions

  Akinori Mori; Tomoteru Mizusaki; Takashi Ikawa; Tomohiro Maegawa; Yasunari Monguchi; Hironao Sajiki

  TETRAHEDRON PERGAMON-ELSEVIER SCIENCE LTD 63 (5) 1270 - 1280 0040-4020 2007/01 [Refereed]
   

  We have found that phenolic hydroxyl groups were readily deoxygenated via aryl sulfonate under the Pd/C-catalyzed hydrogenation conditions in the presence of diethylamine and the method could also be applicable to the hydrodeoxygenation of morphine to afford 3-deoxy-7,8-dihydromorphine. Diethylamine is not only a scavenger of the corresponding methanesulfonic acid derivative, which is produced during the reaction progress, but also a strong promoter of the Pd/C-catalyzed reduction of aryl sulfonates. This catalyst system could provide a general method for the deoxygenation of various phenol derivatives because of its mild reaction conditions, ease of handling, and no need of particular apparatus. (c) 2006 Elsevier Ltd. All rights reserved.
• Mechanistic study of a Pd/C-catalyzed reduction of aryl sulfonates using the Mg-MeOH-NH4OAc system

  Akinori Mori; Tomoteru Mizusaki; Takashi Ikawa; Tomohiro Maegawa; Yasunari Monguchi; Hironao Sajiki

  CHEMISTRY-A EUROPEAN JOURNAL WILEY-V C H VERLAG GMBH 13 (5) 1432 - 1441 0947-6539 2007 [Refereed]
   

  A method for the deoxygenation of phenolic hydroxy groups via aryl triflates or mesylates has been established by using a combination of Pd/C-Mg-MeOH. The addition of NH4OAc to the system markedly accelerated the reaction rate and expanded the scope of the reaction. Mechanistic studies suggested that a single-electron transfer process from the Pd-0 center to the benzene ring is involved in the reduction of aryl sulfonates and that NH4OAc works as a solubilization reagent of the Mg salt and as an accelerator of the electron transfer, thus enhancing the reaction process. Our method was also applicable to the regioselective deuteration of benzene derivatives with CH3OD as the solvent and deuterium source: the original hydroxy group could be efficiently replaced with a deuterium atom.
• Development of a practical and scalable preparation using sonication of Pd/fibroin catalyst for chemoselective hydrogenation

  Yoshiaki Kitamura; Asami Tanaka; Mutsumi Sato; Keiji Oono; Takashi Ikawa; Tomohiro Maegawa; Yasunari Monguchi; Hironao Sajiki

  Synthetic Communications 37 (22) 4381 - 4388 0039-7911 2007/01 [Refereed]
   

  A practical and efficient preparation method of palladium-fibroin (Pd/Fib),
  silk-fibroin-supported Pd(0) by means of sonication, has been developed. The Pd/Fib
  catalyst could be prepared within 12 h at room temperature starting from commercial
  silk-fibroin and Pd(OAc)2 in MeOH, whereas our previous preparation method required
  at least 4 days. The present improved process is applicable to a large-scale preparation
  of Pd/Fib. The Pd/Fib prepared by the present method also catalyzed chemoselective
  hydrogenation of acetylenes, olefins, and azides in the presence of aromatic ketones,
  aldehydes, and halides; N-Cbz protective groups; and benzyl esters, which are
  readily hydrogenated under the Pd/C- or Pd/C(en)-catalyzed hydrogenation
  conditions. @ 2007 Taylor & Francis Group, LLC.
• Chemoselective hydrogenation method catalyzed by Pd/C using diphenylsulfide as a reasonable catalyst poison

  Akinori Mori; Tornoteru Mizusaki; Yurni Miyakawa; Eri Ohashi; Tornoko Haga; Tomohiro Maegawa; Yasunari Monguchi; Hironao Sajiki

  TETRAHEDRON PERGAMON-ELSEVIER SCIENCE LTD 62 (51) 11925 - 11932 0040-4020 2006/12 [Refereed]
   

  While Pd/C is one of the most useful catalysts for hydrogenation, the high catalyst activity of Pd/C causes difficulty in its application to chemoselective hydrogenation between different types of reducible functionalities. In order to achieve chemoselective hydrogenation using Pd/C, we investigated catalyst poison as a controller of the catalyst activity. We found that the addition of Ph2S (diphenylsulfide) to the Pd/C-catalyzed hydrogenation reaction mixture led to reasonable deactivation of Pd/C. By the use of the Pd/C-Ph2S catalytic system, olefins, acetylenes, and azides can be selectively reduced in the coexistence of aromatic carbonyls, aromatic halides, cyano groups, benzyl esters, and N-Cbz (benzyloxycarbonyl) protecting groups. The present method is promising as a general and practical chemoselective hydrogenation process in synthetic organic chemistry. (c) 2006 Elsevier Ltd. All rights reserved.
• General method of obtaining deuterium-labeled heterocyclic compounds using neutral D2O with heterogeneous Pd/C

  Hiroyoshi Esaki; Nobuhiro Ito; Shino Sakai; Tomohiro Maegawa; Yasunari Monguchi; Hironao Sajiki

  TETRAHEDRON PERGAMON-ELSEVIER SCIENCE LTD 62 (47) 10954 - 10961 0040-4020 2006/11 [Refereed]
   

  A protocol of a versatile H-D exchange reaction of heterocyclic compounds catalyzed by heterogeneous Pd/C in D2O is described. The reaction of various nitrogen-containing heterocycles with 10% Pd/C (10 wt % of the substrate) under hydrogen atmosphere in D2O as a deuterium source at 110-180 degrees C for 24 h afforded the corresponding deuterated compounds with satisfactory efficiency of deuteration in moderate to excellent isolated yields. Furthermore, the Pd/C-H-2-D2O system can be extended to the direct deuteration of biologically active compounds such as sulfamethazine, which is used as a synthetic antibacterial drug for fat stocks and would be applied as a general method for the preparation of the standard materials for the analysis of residual chemicals in foods and so on. (c) 2006 Elsevier Ltd. All rights reserved.
• Pd/C-Et3N-mediated catalytic hydrodechlormation of aromatic chlorides under mild conditions

  Yasunari Monguchi; Akira Kume; Kazuyuki Hattori; Tomohiro Maegawa; Hironao Sajiki

  TETRAHEDRON PERGAMON-ELSEVIER SCIENCE LTD 62 (33) 7926 - 7933 0040-4020 2006/08 [Refereed]
   

  A mild and efficient one-pot procedure for the hydrodechlorination of aromatic chlorides using a Pd/C-Et3N system was developed. A variety of aromatic chlorides could be dechlorinated at room temperature and under ambient hydrogen pressure. Et3N activates the catalysis and is likely to work as a single electron donor in this system. (c) 2006 Elsevier Ltd. All rights reserved.
• Pd/C-catalyzed chemoselective hydrogenation in the presence of diphenylsulfide

  Akinori Mori; Yumi Miyakawa; Eri Ohashi; Tomoko Haga; Tomohiro Maegawa; Hironao Sajiki

  ORGANIC LETTERS AMER CHEMICAL SOC 8 (15) 3279 - 3281 1523-7060 2006/07 [Refereed]
   

  A Pd/C-catalyzed chemoselective hydrogenation using diphenylsulfide as a catalyst poison has been developed. This methodology selectively hydrogenates olefin and acetylene functionalities without hydrogenolysis of aromatic carbonyls and halogens, benzyl esters, and N-Cbz protective groups.
• Synergistic effect of a palladium-on-carbon/platinum-on-carbon mixed catalyst in hydrogen/deuterium exchange reactions of alkyl-substituted aromatic compounds

  Nobuhiro Ito; Tsutomu Watahiki; Tsuneaki Maesawa; Tomohiro Maegawa; Hironao Sajiki

  ADVANCED SYNTHESIS & CATALYSIS WILEY-V C H VERLAG GMBH 348 (9) 1025 - 1028 1615-4150 2006/06 [Refereed]
   

  We have found a synergistic effect in the H-D exchange reaction of alkyl-substituted aromatic compounds using the Pd/C-Pt/C-D2O-H-2 system. This system would lead to fully H-D exchange results even on the sterically hindered sites which were only low-deuterium incorporated by Pd/C or Pt/C independently. Since the reaction was general for a variety of aromatic compounds, it could be applied to the deuteration of dianiline derivatives as raw materials for polyimides.
• A mild and facile method for complete hydrogenation of aromatic nuclei in water

  Tomohiro Maegawa; Akira Akashi; Hironao Sajiki

  SYNLETT GEORG THIEME VERLAG KG (9) 1440 - 1442 0936-5214 2006/06 [Refereed]
   

  A mild and complete hydrogenation of aromatic rings catalyzed by heterogeneous 10% Rh/C proceeds at 80 degrees C in water under 5 atm of H-2 pressure. This method is applicable to the hydrogenation of various carbon and heteroaromatic compounds such as alkylbenzenes, biphenyls, pyridines and furans.
• Pd/C-catalyzed deoxygenation of phenol derivatives using Mg metal and MeOH in the presence of NH4OAc

  H Sajiki; A Mori; T Mizusaki; T Ikawa; T Maegawa; K Hirota

  ORGANIC LETTERS AMER CHEMICAL SOC 8 (5) 987 - 990 1523-7060 2006/03 [Refereed]
   

  A Pd/C-catalyzed deoxygenation method of phenolic hydroxyl groups via aryl triflates or mesylates using Mg metal in MeOH at room temperature was developed. The addition of NH4OAc dramatically affects the reactivity and reaction rate. This method is particularly attractive to provide an environmentally benign and widely applicable removal method of phenolic alcohols under quite mild reaction conditions.
• Synthesis of base-selectively deuterium-labelled nucleosides by the Pd/C-catalyzed H-D exchange reaction in deuterium oxide

  H Esaki; F Aoki; T Maegawa; K Hirota; H Sajiki

  HETEROCYCLES PERGAMON-ELSEVIER SCIENCE LTD 66 361 - 369 0385-5414 2005/12 [Refereed]
   

  The D-2 gas-free and base-selective H-D exchange reaction of nucleosides was developed. It discloses a convenient route to the post-synthetic incorporation of deuteriums into the base moiety of nucleic acids with high deuterium efficiency.
• Facile and efficient postsynthetic tritium labeling method catalyzed by Pd/C in HTO.

  Maegawa T; Hirota K; Tatematsu K; Mori Y; Sajiki H

  The Journal of organic chemistry 70 (25) 10581 - 10583 0022-3263 2005/12 [Refereed]
  
• Aromatic ring favorable and efficient H-D exchange reaction catalyzed by Pt/C

  H Sajiki; N Ito; H Esaki; T Maesawa; T Maegawa; K Hirota

  TETRAHEDRON LETTERS PERGAMON-ELSEVIER SCIENCE LTD 46 (41) 6995 - 6998 0040-4039 2005/10 [Refereed]
   

  An effective and applicable Pt/C-catalyzed deuteration method of aromatic rings using D2O as a deuterium source under hydrogen atmosphere was developed. Five percent Pt/C would lead to quite effective H-D exchange results on the aromatic ring systems. The reaction is general for a variety of aromatic compounds including biologically active compounds. (c) 2005 Elsevier Ltd. All rights reserved.
• Erratum: Ligand-free Suzuki-Miyaura reaction catalysed by Pd/C at room temperature (Journal of Chemical Research (2004) (593-595))

  Hironao Sajiki; Takanori Kurita; Atsushi Kozaki; Guolin Zhang; Guolin Zhang; Yoshiaki Kitamura; Tomohiro Maegawa; Kosaku Hirota

  Journal of Chemical Research 344  0308-2342 2005/05

Books etc

• クライン有機化学問題の解き方 : 日本語版

  Klein, David R.; 伊藤, 喬 (Joint translation)東京化学同人 2020/03 9784807909759 6,630p
• 医薬品構造化学 : 薬の構造と薬理作用の関係を紐解く

  前川, 智弘 (Single work)京都廣川書店 2017/03 9784909197054 xxiii, 368p

MISC

• Highly Discriminative and Chemoselective Deprotection/Transformations of Acetals with the Combination of Trialkylsilyl Triflate/2,4,6-Collidine

  Reiya Ohta; Nao Matsumoto; Yoshifumi Ueyama; Yuichi Kuboki; Hiroshi Aoyama; Kenichi Murai; Mitsuhiro Arisawa; Tomohiro Maegawa; Hiromichi Fujioka  Journal of Organic Chemistry  83-  (12)  6432  -6443  2018/06  [Refereed]
  
• The reaction of acetal-type protective groups in combination with TMSOTf and 2,2 '-bipyridyl; mild and chemoselective deprotection and direct conversion to other protective groups

  Hiromichi Fujioka; Yutaka Minamitsuji; Ozora Kubo; Kento Senami; Tomohiro Maegawa  TETRAHEDRON  67-  (16)  2949  -2960  2011/04
• The reaction of acetal-type protective groups in combination with TMSOTf and 2,2 '-bipyridyl; mild and chemoselective deprotection and direct conversion to other protective groups

  Hiromichi Fujioka; Yutaka Minamitsuji; Ozora Kubo; Kento Senami; Tomohiro Maegawa  TETRAHEDRON  67-  (16)  2949  -2960  2011/04
• Palladium on charcoal-catalyzed ligand-free Stille coupling

  Yuki Yabe; Tomohiro Maegawa; Yasunari Monguchi; Hironao Sajiki  TETRAHEDRON  66-  (45)  8654  -8660  2010/11
• Palladium on charcoal-catalyzed ligand-free Stille coupling

  Yuki Yabe; Tomohiro Maegawa; Yasunari Monguchi; Hironao Sajiki  TETRAHEDRON  66-  (45)  8654  -8660  2010/11
• Synthesis of deuterium-labelled drugs by hydrogen-deuterium (H-D) exchange using heterogeneous catalysis

  Nkaelang Modutlwa; Tomohiro Maegawa; Yasunari Monguchi; Hironao Sajiki  JOURNAL OF LABELLED COMPOUNDS & RADIOPHARMACEUTICALS  53-  (11-12)  686  -692  2010/09
• Synthesis of deuterium-labelled drugs by hydrogen-deuterium (H-D) exchange using heterogeneous catalysis

  Nkaelang Modutlwa; Tomohiro Maegawa; Yasunari Monguchi; Hironao Sajiki  JOURNAL OF LABELLED COMPOUNDS & RADIOPHARMACEUTICALS  53-  (11-12)  686  -692  2010/09
• Mild and highly chemoselective deprotection of methoxymethyl (MOM) ethers in combination with TMSOTf (TESOTf)-2,2 '-bipyridyl

  Tomohiro Maegawa; Ozora Kubo; Kento Senami; Yutaka Minamitsuji; Hiromichi Fujioka  ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY  240-  2010/08
• Palladium on Carbon-Catalyzed Synthesis of Benzil Derivatives from 1,2-Diarylalkynes with DMSO and Molecular Oxygen as Dual Oxidants

  Shigeki Mori; Masato Takubo; Takayoshi Yanase; Tomohiro Maegawa; Yasunari Monguchi; Hironao Sajiki  ADVANCED SYNTHESIS & CATALYSIS  352-  (10)  1630  -1634  2010/07
• Palladium on Carbon-Catalyzed Synthesis of Benzil Derivatives from 1,2-Diarylalkynes with DMSO and Molecular Oxygen as Dual Oxidants

  Shigeki Mori; Masato Takubo; Takayoshi Yanase; Tomohiro Maegawa; Yasunari Monguchi; Hironao Sajiki  ADVANCED SYNTHESIS & CATALYSIS  352-  (10)  1630  -1634  2010/07
• Ligand-Free and Heterogeneous Palladium on Carbon-Catalyzed Hetero-Suzuki-Miyaura Cross-Coupling

  Yoshiaki Kitamura; Satoko Sako; Azusa Tsutsui; Yasunari Monguchi; Tomohiro Maegawa; Yukio Kitade; Hironao Sajiki  ADVANCED SYNTHESIS & CATALYSIS  352-  (4)  718  -730  2010/03
• Mild Deprotection of Methylene Acetals in Combination with Trimethylsilyl Triflate-2,2 '-Bipyridyl

  Hiromichi Fujioka; Kento Senami; Ozora Kubo; Kenzo Yahata; Yutaka Minamitsuji; Tomohiro Maegawa  CHEMICAL & PHARMACEUTICAL BULLETIN  58-  (3)  426  -428  2010/03
• Ligand-Free and Heterogeneous Palladium on Carbon-Catalyzed Hetero-Suzuki-Miyaura Cross-Coupling

  Yoshiaki Kitamura; Satoko Sako; Azusa Tsutsui; Yasunari Monguchi; Tomohiro Maegawa; Yukio Kitade; Hironao Sajiki  ADVANCED SYNTHESIS & CATALYSIS  352-  (4)  718  -730  2010/03
• Mild Deprotection of Methylene Acetals in Combination with Trimethylsilyl Triflate-2,2 '-Bipyridyl

  Hiromichi Fujioka; Kento Senami; Ozora Kubo; Kenzo Yahata; Yutaka Minamitsuji; Tomohiro Maegawa  CHEMICAL & PHARMACEUTICAL BULLETIN  58-  (3)  426  -428  2010/03
• C-C BOND FORMATION ON 5-POSITION OF URIDINE RING BY MORITA-BAYLIS-HILLMAN TYPE REACTION

  Yasunari Monguchi; Kanoko Yasunaga; Takashi Tsunoda; Takayuki Ando; Tomohiro Maegawa; Kosaku Hirota; Hironao Sajiki  HETEROCYCLES  80-  (1)  537  -555  2010/01
• Copper-Mediated Reductive Amination of Aryl Halides with Trimethylsilyl Azide

  Yasunari Monguchi; Toshihide Maejima; Shigeki Mori; Tomohiro Maegawa; Hironao Sajiki  CHEMISTRY-A EUROPEAN JOURNAL  16-  (25)  7372  -7375  2010
• Palladium on carbon-catalyzed synthesis of 2-and 2,3-substituted indoles under heterogeneous conditions

  Yasunari Monguchi; Shigeki Mori; Satoka Aoyagi; Azusa Tsutsui; Tomohiro Maegawa; Hironao Sajiki  ORGANIC & BIOMOLECULAR CHEMISTRY  8-  (14)  3338  -3342  2010
• Remarkable effect of phosphine on the reactivity of O,P-acetal-efficient substitution reaction of O,P-acetal

  Hiromichi Fujioka; Akihiro Goto; Kazuki Otake; Ozora Kubo; Kenzo Yahata; Yoshinari Sawama; Tomohiro Maegawa  CHEMICAL COMMUNICATIONS  46-  (22)  3976  -3978  2010
• C-C BOND FORMATION ON 5-POSITION OF URIDINE RING BY MORITA-BAYLIS-HILLMAN TYPE REACTION

  Yasunari Monguchi; Kanoko Yasunaga; Takashi Tsunoda; Takayuki Ando; Tomohiro Maegawa; Kosaku Hirota; Hironao Sajiki  HETEROCYCLES  80-  (1)  537  -555  2010/01
• Copper-Mediated Reductive Amination of Aryl Halides with Trimethylsilyl Azide

  Yasunari Monguchi; Toshihide Maejima; Shigeki Mori; Tomohiro Maegawa; Hironao Sajiki  CHEMISTRY-A EUROPEAN JOURNAL  16-  (25)  7372  -7375  2010
• Palladium on carbon-catalyzed synthesis of 2-and 2,3-substituted indoles under heterogeneous conditions

  Yasunari Monguchi; Shigeki Mori; Satoka Aoyagi; Azusa Tsutsui; Tomohiro Maegawa; Hironao Sajiki  ORGANIC & BIOMOLECULAR CHEMISTRY  8-  (14)  3338  -3342  2010
• Remarkable effect of phosphine on the reactivity of O,P-acetal-efficient substitution reaction of O,P-acetal

  Hiromichi Fujioka; Akihiro Goto; Kazuki Otake; Ozora Kubo; Kenzo Yahata; Yoshinari Sawama; Tomohiro Maegawa  CHEMICAL COMMUNICATIONS  46-  (22)  3976  -3978  2010
• Novel Regiocontrolled Protection of 1,2- and 1,3-Diols via Mild Cleavage of Methylene Acetals

  Hiromichi Fujioka; Kento Senami; Ozora Kubo; Kenzo Yahata; Yutaka Minamitsuji; Tomohiro Maegawa  ORGANIC LETTERS  11-  (22)  5138  -5141  2009/11
• Novel Regiocontrolled Protection of 1,2- and 1,3-Diols via Mild Cleavage of Methylene Acetals

  Hiromichi Fujioka; Kento Senami; Ozora Kubo; Kenzo Yahata; Yutaka Minamitsuji; Tomohiro Maegawa  ORGANIC LETTERS  11-  (22)  5138  -5141  2009/11
• Development of Molecular Sieves-Supported Palladium Catalyst and Chemoselective Hydrogenation of Unsaturated Bonds in the Presence of Nitro Groups

  Tomohiro Maegawa; Tohru Takahashi; Masatoshi Yoshimura; Hiroyasu Suzuka; Yasunari Monguchi; Hironao Sajiki  ADVANCED SYNTHESIS & CATALYSIS  351-  (13)  2091  -2095  2009/09
• Bimetallic Palladium-Platinum-on-Carbon-Catalyzed H-D Exchange Reaction: Synergistic Effect on Multiple Deuterium Incorporation

  Tomohiro Maegawa; Nobuhiro Ito; Keiji Oono; Yasunari Monguchi; Hironao Sajiki  SYNTHESIS-STUTTGART  2674-2678-  (16)  2674  -2678  2009/08
• Bimetallic Palladium-Platinum-on-Carbon-Catalyzed H-D Exchange Reaction: Synergistic Effect on Multiple Deuterium Incorporation

  Tomohiro Maegawa; Nobuhiro Ito; Keiji Oono; Yasunari Monguchi; Hironao Sajiki  SYNTHESIS-STUTTGART  2674-2678-  (16)  2674  -2678  2009/08
• Palladium on charcoal-catalyzed ligand free Stille coupling

  Yuki Yabe; Yuki Fujita; Tomohiro Maegawa; Yasunari Monguchi; Hironao Sajiki  ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY  238-  2009/08
• Multiple/regioselective H-D exchange reaction of aliphatic alkanes and alcohols

  Yuta Fujiwara; Hiroyoshi Esaki; Tomohiro Maegawa; Yasunari Monguchi; Hironao Sajiki  ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY  238-  2009/08
• Pd(0)-polyethyleneimine complex as a partial hydrogenation catalyst of alkynes to alkenes

  Shigeki Mori; Tomoyuki Ohkubo; Takashi Ikawa; Akira Kume; Tomohiro Maegawa; Yasunari Monguchi; Hironao Sajiki  JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL  307-  (1-2)  77  -87  2009/07
• Pd(0)-polyethyleneimine complex as a partial hydrogenation catalyst of alkynes to alkenes

  Shigeki Mori; Tomoyuki Ohkubo; Takashi Ikawa; Akira Kume; Tomohiro Maegawa; Yasunari Monguchi; Hironao Sajiki  JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL  307-  (1-2)  77  -87  2009/07
• IODOBENZENE DIACETATE-PROMOTED N-N AND N-O BOND FORMATION FOR PYRAZOLO- AND ISOXAZOLOPYRIMIDINE SYNTHESES

  Yasunari Monguchi; Kazuyuki Hattori; Tomohiro Maegawa; Kosaku Hirota; Hironao Sajiki  HETEROCYCLES  79-  669  -680  2009/04
• IODOBENZENE DIACETATE-PROMOTED N-N AND N-O BOND FORMATION FOR PYRAZOLO- AND ISOXAZOLOPYRIMIDINE SYNTHESES

  Yasunari Monguchi; Kazuyuki Hattori; Tomohiro Maegawa; Kosaku Hirota; Hironao Sajiki  HETEROCYCLES  79-  669  -680  2009/04
• Temperature-dependent suppression of palladium on carbon-catalyzed hydrogenations

  Utpal Bora; Kiichiro Yaguchi; Akira Kume; Tomohiro Maegawa; Yasunari Monguchi; Hironao Sajiki  CATALYSIS COMMUNICATIONS  10-  (8)  1161  -1165  2009/03
• Novel deprotection method of Fmoc group under neutral hydrogenation conditions

  Tomohiro Maegawa; Yuta Fujiwara; Takashi Ikawa; Hideo Hisashi; Yasunari Monguchi; Hironao Sajiki  AMINO ACIDS  36-  (3)  493  -499  2009/03
• Temperature-dependent suppression of palladium on carbon-catalyzed hydrogenations

  Utpal Bora; Kiichiro Yaguchi; Akira Kume; Tomohiro Maegawa; Yasunari Monguchi; Hironao Sajiki  CATALYSIS COMMUNICATIONS  10-  (8)  1161  -1165  2009/03
• Novel deprotection method of Fmoc group under neutral hydrogenation conditions

  Tomohiro Maegawa; Yuta Fujiwara; Takashi Ikawa; Hideo Hisashi; Yasunari Monguchi; Hironao Sajiki  AMINO ACIDS  36-  (3)  493  -499  2009/03
• ORGN 469-Selective conversion of nitrile derivatives to secondary or tertiary amines

  Yuki Fujita; Eri Murakami; Tomohiro Maegawa; Yasunari Monguchi; Hironao Sajiki  ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY  237-  2009/03
• COPPER/HP20: NOVEL AND POLYMER-SUPPORTED COPPER CATALYST FOR HUISGEN CYCLOADDITION

  Yoshiaki Kitamura; Kazumi Taniguchi; Tomohiro Maegawa; Yasunari Monguchi; Yukio Kitade; Hironao Sajiki  HETEROCYCLES  77-  (1)  521  -532  2009/01
• A Highly Active Heterogeneous Palladium Catalyst Supported on a Synthetic Adsorbent

  Yasunari Monguchi; Yuki Fujita; Koichi Endo; Shinobu Takao; Masatoshi Yoshimura; Yukio Takagi; Tomohiro Maegawa; Hironao Sajiki  CHEMISTRY-A EUROPEAN JOURNAL  15-  (4)  834  -837  2009
• A simple and efficient oxidation of alcohols with ruthenium on carbon

  Shigeki Mori; Masato Takubo; Kazuya Makida; Takayoshi Yanase; Satoka Aoyagi; Tomohiro Maegawa; Yasunari Monguchi; Hironao Sajiki  CHEMICAL COMMUNICATIONS  5159-5161-  (34)  5159  -5161  2009
• Remarkable effect of 2,2 '-bipyridyl: mild and highly chemoselective deprotection of methoxymethyl (MOM) ethers in combination with TMSOTf (TESOTf)-2,2 '-bipyridyl

  Hiromichi Fujioka; Ozora Kubo; Kento Senami; Yutaka Minamitsuji; Tomohiro Maegawa  CHEMICAL COMMUNICATIONS  4429-4431-  (29)  4429  -4431  2009
• Efficient and Practical Arene Hydrogenation by Heterogeneous Catalysts under Mild Conditions

  Tomohiro Maegawa; Akira Akashi; Kiichiro Yaguchi; Yohei Iwasaki; Masahiro Shigetsura; Yasunari Monguchi; Hironao Sajiki  CHEMISTRY-A EUROPEAN JOURNAL  15-  (28)  6953  -6963  2009
• COPPER/HP20: NOVEL AND POLYMER-SUPPORTED COPPER CATALYST FOR HUISGEN CYCLOADDITION

  Yoshiaki Kitamura; Kazumi Taniguchi; Tomohiro Maegawa; Yasunari Monguchi; Yukio Kitade; Hironao Sajiki  HETEROCYCLES  77-  (1)  521  -532  2009/01
• A Highly Active Heterogeneous Palladium Catalyst Supported on a Synthetic Adsorbent

  Yasunari Monguchi; Yuki Fujita; Koichi Endo; Shinobu Takao; Masatoshi Yoshimura; Yukio Takagi; Tomohiro Maegawa; Hironao Sajiki  CHEMISTRY-A EUROPEAN JOURNAL  15-  (4)  834  -837  2009
• A simple and efficient oxidation of alcohols with ruthenium on carbon

  Shigeki Mori; Masato Takubo; Kazuya Makida; Takayoshi Yanase; Satoka Aoyagi; Tomohiro Maegawa; Yasunari Monguchi; Hironao Sajiki  CHEMICAL COMMUNICATIONS  5159-5161-  (34)  5159  -5161  2009
• Remarkable effect of 2,2 '-bipyridyl: mild and highly chemoselective deprotection of methoxymethyl (MOM) ethers in combination with TMSOTf (TESOTf)-2,2 '-bipyridyl

  Hiromichi Fujioka; Ozora Kubo; Kento Senami; Yutaka Minamitsuji; Tomohiro Maegawa  CHEMICAL COMMUNICATIONS  4429-4431-  (29)  4429  -4431  2009
• Efficient and Practical Arene Hydrogenation by Heterogeneous Catalysts under Mild Conditions

  Tomohiro Maegawa; Akira Akashi; Kiichiro Yaguchi; Yohei Iwasaki; Masahiro Shigetsura; Yasunari Monguchi; Hironao Sajiki  CHEMISTRY-A EUROPEAN JOURNAL  15-  (28)  6953  -6963  2009
• Evaluation of Aromatic Amination Catalyzed by Palladium on Carbon: A Practical Synthesis of Triarylamines

  Yasunari Monguchi; Katsunori Kitamoto; Takashi Ikawa; Tomohiro Maegawa; Hironao Sajiki  ADVANCED SYNTHESIS & CATALYSIS  350-  (17)  2767  -2777  2008/11
• Evaluation of Aromatic Amination Catalyzed by Palladium on Carbon: A Practical Synthesis of Triarylamines

  Yasunari Monguchi; Katsunori Kitamoto; Takashi Ikawa; Tomohiro Maegawa; Hironao Sajiki  ADVANCED SYNTHESIS & CATALYSIS  350-  (17)  2767  -2777  2008/11
• A Convenient and Effective Method for the Regioselective Deuteration of Alcohols

  Tomohiro Maegawa; Yuta Fujiwara; Yuya Inagaki; Yasunari Monguchi; Hironao Sajiki  ADVANCED SYNTHESIS & CATALYSIS  350-  (14-15)  2215  -2218  2008/10
• A Convenient and Effective Method for the Regioselective Deuteration of Alcohols

  Tomohiro Maegawa; Yuta Fujiwara; Yuya Inagaki; Yasunari Monguchi; Hironao Sajiki  ADVANCED SYNTHESIS & CATALYSIS  350-  (14-15)  2215  -2218  2008/10
• ORGN 25-Facile and efficient construction of cyclohexane derivatives by hydrogenation of aromatic ring

  Tomohiro Maegawa; Kiichiro Yaguchi; Akira Akashi; Yasunari Monguchi; Hironao Sajiki  ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY  236-  2008/08
• ORGN 220-Heterogeneous Pd/C-catalyzed Hiyama cross-coupling reaction

  Takayoshi Yanase; Shigeki Mori; Satoka Aoyagi; Tomohiro Maegawa; Yasunari Monguchi; Hironao Sajiki  ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY  236-  2008/08
• Mild and efficient H/D exchange of alkanes based on C-H activation catalyzed by rhodium on charcoal

  Tomohiro Maegawa; Yuta Fujiwara; Yuya Inagaki; Hiroyoshi Esaki; Yasunari Monguchi; Hironao Sajlki  ANGEWANDTE CHEMIE-INTERNATIONAL EDITION  47-  (29)  5394  -5397  2008
• Mild and efficient H/D exchange of alkanes based on C-H activation catalyzed by rhodium on charcoal

  Tomohiro Maegawa; Yuta Fujiwara; Yuya Inagaki; Hiroyoshi Esaki; Yasunari Monguchi; Hironao Sajlki  ANGEWANDTE CHEMIE-INTERNATIONAL EDITION  47-  (29)  5394  -5397  2008
• Efficient and convenient heterogeneous palladium-catalyzed regioselective deuteration at the benzylic position

  Thkanori Kurita; Kazuyuki Hattori; Saori Seki; Mikuto Mizumoto; Fumiyo Aoki; Yuki Yamada; Kanoko Ikawa; Tomohiro Maegawa; Yasunari Monguchi; Hironao Sajiki  CHEMISTRY-A EUROPEAN JOURNAL  14-  (2)  664  -673  2008
• Pd/C-catalyzed Direct α-Oxygenation of 1,3-Dicarbonyl compounds Using molecular Oxygen.

  Yasunari Monguchi; Tohru Takahashi; Yusuke Iida; Yuta Fujiwara; Yuya Inagaki; Tomohiro Maegawa; Hironao Sajiki  Synlett  2291  -2294  2008
• Partial hydrogenation of alkynes to cis-olefins by using a novel Pd(0)-polyethyleneimine catalyst.

  Hironao Sajiki; Shigeki Mori; Tomoyuki Ohkubo; Takashi Ikawa; Akira Kume; Tomohiro Maegawa; Yasunari Monguchi  Chemistry (Weinheim an der Bergstrasse, Germany)  14-  (17)  5109  -5111  2008
• H-D Exchange Reaction Taking Advantage of a Synergistic Effect of a Heterogeneous Pd and Pt Mixed Catalyst.

  Nobuhiro Ito; Tsutomu Watahiki; Tsuneaki Maesawa; Tomohiro Maegawa; Hironao Sajiki  Synthesis  1467  -1478  2008
• Facile and Convenient Method of Deuterium Gas Generation via Pd/C-catalyzed H2–D2 Exchange Reaction and Its Application to Synthesis of Deuterium-Labelled Compounds(共著)

  KURITA Takanori; AOKI Fumiyo; MIZUMOTO Takuto; MAEJIMA Toshihide; ESAKI Hiroyoshi; MAEGAWA Tomohiro; MONGUCHI Yasunari; SAJIKI Hironao  Chem. Eur. J.  14-  (11)  3371  -3379  2008
• An efficient deuteration method catalyzed by heterogeneous platinum group metals

  Hiroyoshi Esaki; Takanori Kurita; Yuta Fujiwara; Tomohiro Maegawa; Yasunari Monguchi; Hironao Sajiki  JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY JAPAN  65-  (12)  1179  -1190  2007/12
• ORGN 77-Chemoselective and mild hydrogenation methods catalyzed by heterogeneous Pd/C-ethylendiamine, Pd-fibroin or Pd-polyethyleneimine complexes

  Hironao Sajiki; Shigeki Mori; Yoshiaki Kitamura; Takashi Ikawa; Yasunari Monguchi; Tomohiro Maegawa  ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY  234-  2007/08
• ORGN 538-Ligand-free and heterogeneous Pd/C catalyzed Suzuki-Miyaura coupling reaction toward the synthesis of heterobiaryl derivatives

  Satoko Sako; Yoshiaki Kitamura; Takahiro Udzu; Tomohiro Maegawa; Yasunari Monguchi; Hironao Sajiki  ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY  234-  2007/08
• Heterogeneous Pd/C-catalyzed aromatic amination

  Yasunari Monguchi; Katsunori Kitamoto; Shigeki Mori; Takayoshi Yanase; Yuiko Mizoguchi; Takashi Ikawa; Tomohiro Maegawa; Hironao Sajiki  ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY  233-  2007/03
• Novel redox reactions between sec-alcohols and ketones using Pd/C-H2O-D2O

  Hiroyoshi Esaki; Rumi Ohtaki; Tomohiro Maegawa; Yasunari Monguchi; Hironao Sajiki  ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY  233-  2007/03
• Efficient H/D exchange reactions of alkyl-substituted benzene derivatives by means of the Pd/C-H-2-D2O system

  Hiroyoshi Esaki; Fumiyo Aoki; Miho Umemura; Masatsugu Kato; Tomohiro Maegawa; Yasunari Monguchi; Hironao Sajiki  CHEMISTRY-A EUROPEAN JOURNAL  13-  (14)  4052  -4063  2007
• スチレン類の触媒的ジアルコキシル化反応

  前川 智弘  ファルマシア  42-  (10)  1023  -1024  2006/10
• ORGN 204-Development of environmentally friendly alkylation method of amines using nitrile as an alkylating agent

  Yuki Fujita; Takashi Ikawa; Tomohiro Maegawa; Hironao Sajiki  ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY  232-  2006/09
• ORGN 270-Mild and phosphine-free Suzuki-Miyaura coupling reaction catalyzed by Pd/C

  Yoshiaki Kitamura; Satoko Sako; Takahiro Udzu; Ai Sakurai; Asami Tanaka; Yusuke Kobayashi; Utpal Bora; Takanori Kurita; Atsushi Kozaki; Tomohiro Maegawa; Hironao Sajiki  ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY  232-  2006/09
• ORGN 194-Development of novel heterogeneous catalyst Pd/C[Ph2S] for chemoselective hydrogenation

  Tomoteru Mizusaki; Akinori Mori; Yukio Takagi; Tomohiro Maegawa; Yasunari Monguchi; Hironao Sajiki  ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY  232-  2006/09
• ORGN 689-Pd/C(en)-catalyzed benzylic site selective H-D exchange reaction of O-benzyl protective group

  Takanori Kurita; Tomohiro Maegawa; Yasunari Monguchi; Hironao Sajiki  ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY  232-  2006/09
• Pd/C-catalyzed chemoselective hydrogenation using diphenylsulfide

  Akinori Mori; Tomohiro Maegawa; Hironao Sajiki; Kosaku Hirota  ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY  231-  2006/03
• Facile and efficient isotope labeling method for phenylalanine derivatives catalyzed by Pd/C

  T Maegawa; A Akashi; H Esaki; F Aoki; H Sajiki; K Hirota; K Tatematsu; Y Mori  ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY  230-  U2584  -U2584  2005/08
• Efficient deuterium labeling method of biologically active compounds

  H Esaki; F Aoki; T Maegawa; H Sajiki; K Hirota  ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY  230-  U2582  -U2583  2005/08
• Palladium-catalyzed base-selective H-D exchange reaction of nucleosides in deuterium oxide

  H Sajiki; H Esaki; F Aoki; T Maegawa; K Hirota  SYNLETT  1385-1388-  (9)  1385  -1388  2005/06
• Ligand-free Suzuki-Miyaura reaction catalysed by Pd/C at room temperature (pg 593, 2004)

  H Sajiki; T Kurita; A Kozaki; GL Zhang; Y Kitamura; T Maegawa; K Hirota  JOURNAL OF CHEMICAL RESEARCH-S  (5)  344  -344  2005/05
• Efficient protocol for the phosphine-free Suzuki-Miyaura reaction catalyzed by palladium on carbon at room temperature (Mar, pg 537, 2005)

  H Sajiki; T Kurita; A Kozaki; G Zhang; Y Kitamura; T Maegawa; K Hirota  SYNTHESIS-STUTTGART  852-  (5)  852  -852  2005/04
• Easy, copper-, ligand- and amine-free sonogashira coupling reaction catalyzed by palladium on carbon at low catalyst loading and by exposure to air (March, pg 619, 2005)

  H Sajiki; G Zhang; Y Kitamura; T Maegawa; K Hirota  SYNLETT  (6)  1046  -1046  2005/04
• Easy copper-, ligand- and amine-free sonogashira coupling reaction catalyzed by palladium on carbon at low catalyst loading and by exposure to air

  GL Zhang  SYNLETT  1046-  (4)  619  -622  2005/03
• Efficient and selective deuteration of phenylalanine derivatives catalyzed by Pd/C

  T Maegawa; A Akashi; H Esaki; F Aoki; H Sajiki; K Hirota  SYNLETT  845-847-  (5)  845  -847  2005/03
• Complete replacement of H-2 by D-2 via Pd/C-catalyzed H/D exchange reaction

  H Sajiki; T Kurita; H Esaki; F Aoki; T Maegawa; K Hirota  ORGANIC LETTERS  6-  (20)  3521  -3523  2004/09
• Efficient C-H/C-D exchange reaction on the alkyl side chain of aromatic compounds using heterogeneous Pd/C in D2O

  H Sajiki; F Aoki; H Esaki; T Maegawa; K Hirota  ORGANIC LETTERS  6-  (9)  1485  -1487  2004/04
• Preparation and reactivity of 1,3,5,7-tetrakis[4-(diacetoxyiodo)phenyl]adamantane, a recyclable hypervalent iodine(III) reagent

  H Tohma; A Maruyama; A Maeda; T Maegawa; T Dohi; M Shiro; T Morita; Y Kita  ANGEWANDTE CHEMIE-INTERNATIONAL EDITION  43-  (27)  3595  -3598  2004
• A novel and direct synthesis of alkylated 2,2 '-bithiophene derivatives using a combination of hypervalent iodine(III) reagent and BF3 center dot Et2O

  H Tohma; M Iwata; T Maegawa; Y Kiyono; A Maruyama; Y Kita  ORGANIC & BIOMOLECULAR CHEMISTRY  1-  (10)  1647  -1649  2003/05
• A novel and direct synthesis of alkylated 2,2 '-bithiophene derivatives using a combination of hypervalent iodine(III) reagent and BF3 center dot Et2O

  H Tohma; M Iwata; T Maegawa; Y Kiyono; A Maruyama; Y Kita  ORGANIC & BIOMOLECULAR CHEMISTRY  1-  (10)  1647  -1649  2003/05
• Facile and efficient oxidative transformation of primary alcohols to methyl esters in water using hypervalent iodine(III) reagents

  H Tohma; T Maegawa; Y Kita  SYNLETT  (5), 723-725-  (5)  723  -725  2003/04
• Facile and efficient oxidative transformation of primary alcohols to methyl esters in water using hypervalent iodine(III) reagents

  H Tohma; T Maegawa; Y Kita  SYNLETT  (5), 723-725-  (5)  723  -725  2003/04
• Facile and efficient oxidation of sulfides to sulfoxides in water using hypervalent iodine reagents

  H Tohma; T Maegawa; Y Kita  ARKIVOC  (6), 62-70-  62  -70  2003
• Palladium-catalyzed H-D exchange into nucleic acids in deuterium oxide.

  Hironao Sajiki; Fumiyo Aoki; Hiroyoshi Esaki; Tomohiro Maegawa; Kosaku Hirota  Nucleic acids research. Supplement (2001)  (3), 55-56-  (3)  55  -56  2003
• Facile and efficient oxidation of sulfides to sulfoxides in water using hypervalent iodine reagents

  H Tohma; T Maegawa; Y Kita  ARKIVOC  (6), 62-70-  62  -70  2003
• Palladium-catalyzed H-D exchange into nucleic acids in deuterium oxide.

  Hironao Sajiki; Fumiyo Aoki; Hiroyoshi Esaki; Tomohiro Maegawa; Kosaku Hirota  Nucleic acids research. Supplement (2001)  (3), 55-56-  (3)  55  -56  2003
• Novel and efficient oxidative biaryl coupling reaction of alkylarenes using a hypervalent iodine(III) reagent

  Hirofumi Tohma; Minako Iwata; Tomohiro Maegawa; Yasuyuki Kita  Tetrahedron Letters  43-  (50)  9241  -9244  2002/12
• Novel and efficient oxidative biaryl coupling reaction of alkylarenes using a hypervalent iodine(III) reagent

  H Tohma; M Iwata; T Maegawa; Y Kita  TETRAHEDRON LETTERS  43-  (50)  9241  -9244  2002/12
• Facile and clean oxidation of alcohols in water using hypervalent iodine(III) reagents

  H Tohma; T Maegawa; S Takizawa; Y Kita  ADVANCED SYNTHESIS & CATALYSIS  344-  (3-4)  328  -337  2002/05
• Facile and clean oxidation of alcohols in water using hypervalent iodine(III) reagents

  H Tohma; T Maegawa; S Takizawa; Y Kita  ADVANCED SYNTHESIS & CATALYSIS  344-  (3-4)  328  -337  2002/05
• Novel catalytic asymmetric sulfoxidation in water using the hypervalent iodine reagent iodoxybenzene

  H Tohma; S Takizawa; H Morioka; T Maegawa; Y Kita  CHEMICAL & PHARMACEUTICAL BULLETIN  48-  (3)  445  -446  2000/03
• Novel catalytic asymmetric sulfoxidation in water using the hypervalent iodine reagent iodoxybenzene

  H Tohma; S Takizawa; H Morioka; T Maegawa; Y Kita  CHEMICAL & PHARMACEUTICAL BULLETIN  48-  (3)  445  -446  2000/03
• Facile and clean oxidation of alcohols in water using hypervalent iodine(III) reagents

  H Tohma; S Takizawa; T Maegawa; Y Kita  ANGEWANDTE CHEMIE-INTERNATIONAL EDITION  39-  (7)  1306  -+  2000
• Facile and clean oxidation of alcohols in water using hypervalent iodine(III) reagents

  H Tohma; S Takizawa; T Maegawa; Y Kita  ANGEWANDTE CHEMIE-INTERNATIONAL EDITION  39-  (7)  1306  -+  2000
• Novel one-pot preparation of 5-methoxylated indoline and indole derivatives using a hypervalent iodine(III) reagent

  H Tohma; H Watanabe; S Takizawa; T Maegawa; Y Kita  HETEROCYCLES  51-  (8)  1785  -1788  1999/08
• Novel one-pot preparation of 5-methoxylated indoline and indole derivatives using a hypervalent iodine(III) reagent

  H Tohma; H Watanabe; S Takizawa; T Maegawa; Y Kita  HETEROCYCLES  51-  (8)  1785  -1788  1999/08
• Hypervalent iodine(V)-induced asymmetric oxidation of sulfides to sulfoxides mediated by reversed micelles: Novel nonmetallic catalytic system

  H Tohma; S Takizawa; H Watanabe; Y Fukuoka; T Maegawa; Y Kita  JOURNAL OF ORGANIC CHEMISTRY  64-  (10)  3519  -3523  1999/05
• Hypervalent iodine(V)-induced asymmetric oxidation of sulfides to sulfoxides mediated by reversed micelles: Novel nonmetallic catalytic system

  H Tohma; S Takizawa; H Watanabe; Y Fukuoka; T Maegawa; Y Kita  JOURNAL OF ORGANIC CHEMISTRY  64-  (10)  3519  -3523  1999/05

Awards & Honors

• 2020/08 Kansai Branch, The Society of Synthetic Organic Chemistry Kansai Branch Award of The Society of Synthetic Organic Chemistry
   Development of novel reactions utilizing elemental properties of phosphorus and sulfur atoms
• 2009 プロセス化学会 2009JSPC優秀賞
   メチレンアセタールの非常に緩和で高選択的な脱保護法の開発 

  受賞者: 藤岡弘道;瀬波賢人;久保大空;南辻裕;前川智弘
• 2008 有機合成化学協会 東海支部 平成20年度有機合成化学協会東海支部奨励賞
   白金族系触媒を用いた水素同位体標識化法の応用と芳香環水素化反応の開発 

  受賞者: 前川 智弘

Research Grants & Projects

• 硫黄化合物を用いる高活性なハロゲン化反応の開発とその応用

  文部科学省：科学研究費補助金(基盤研究(C))

  Date (from‐to) : 2018/04 -2022/03 

  Author : 前川 智弘
• メチレンアセタールの新たな反応性の開拓とその複素環合成への応用

  文部科学省：科学研究費補助金(基盤研究(C))

  Date (from‐to) : 2014 -2016 

  Author : 前川 智弘
• 多様なヘテロ４員環及び５員環化合物の合成法の開発と生物活性天然物合成への応用

  文部科学省：科学研究費補助金(若手研究(B))

  Date (from‐to) : 2012 -2013 

  Author : 前川 智弘

   

  ルイス酸存在下、MOMエーテルとトリメチルホスファイトから得られるO,P-アセタールを鍵中間体として、ジメチル基などの生物学的等価体として注目を集める4員環化合物であるオキセタン‐3‐オンならびに天然物中にみられる5員環化合物であるオキソラン-3-オンの効率的な合成法の開発に成功した。環構築後に残存するリン原子を活用して種々のアルデヒドとのHorner-Wadsworth-Emmons反応により、様々な置換基を有する多様な誘導体の簡便合成が可能である。また、出発原料をN,P-アセタールに代えることで、アゼチジン‐3‐オン、ピロリジン‐3‐オン誘導体を効率的に合成することにも成功した。さらに本法を応用し、抗腫瘍活性を有するpseudodeflectusinの短工程かつ高収率での合成を達成することができた。
• ホスホニウム塩中間体を利用する有機合成化学：新規基盤反応の開発と天然物合成への応用

  武田科学振興財団：薬学系研究奨励

  Date (from‐to) : 2011 -2013 

  Author : 前川 智弘
• Pd-Pt/C複合触媒を用いた高効率的重水素化反応の開発

  文部科学省：科学研究費補助金(若手研究(B))

  Date (from‐to) : 2005 -2006 

  Author : 前川 智弘

   

  タンパク質や酵素等の高次構造解析や反応機構の解明等に用いられる重水素(D)標識化合物は小分子量のD標識シントンやH-D交換反応等により合成されるが、いずれの手法も手間がかかる、高価な試薬・特殊な反応条件を必要とするなどの問題点を有している。一方、当研究室ではこれまでにPd/C-D_2O-H_2の組み合わせによる簡便重水素化法の開発に成功し、一般性ある高効率的D標識体合成法として確立している。また、Pt/C存在下では芳香環上でのD化反応が優先的に進行することを見出し、さらにPd/C及びPt/C共存下では芳香環及びアルキル炭素上でのD化反応が同時に進行し1段階での多重D化反応が進行することを見出している。そこでより効率的なD化法並びにD化触媒の開発を目的として異なる触媒反応点を有するPdとPtを活性炭に同時に担持させた複合金属触媒の調製及び反応性の検討を行った。まず触媒を調製するにあたり、触媒の調製法による反応性の違いについて検討した。一般にPdの活性炭担持型触媒の調製法としては2価のPd金属の溶液中に活性炭を加えた後、還元剤で0価に還元する方法により調製する。そこで今回、より高活性な複合触媒の調製を目的として、還元剤に水素、ヒドラジン、ホルムアルデヒド、水素化ホウ素ナトリウムの4種を用いて触媒を調製したところ、水素化ホウ素ナトリウムを還元剤に用いて調製した触媒が最も高い活性を示し、芳香環、アルキル側鎖共に高効率的にD化を受けることが明らかとなった。また、本触媒はD化反応において相乗効果が発現することが明らかとなり、Pd/CまたはPt/Cを単独で用いた場合よりも高い重水素化率で反応が進行し、特に立体的に込み合った部位での重水素化が効率的に進行することを明らかとした。
• Efficient and facile C-H/C-D exchange reaction of organic compounds using heterogeneous Pd/C.

  Date (from‐to) : 2003 -2006

Others

• 2015/04 -2015/04  Transition metal catalyzed chalcone synthesis using direct coupling reaction 

  We developed a novel chalcone synthesis using direct coupling reaction of vinyl ketone and aromatic ring without any halogen atom.

Other link

researchmap

https://researchmap.jp/read0198565