Development of synthetic methods of multisubstituted heterocycliccompounds by catalytic addition of carbon-heteroatom bonds

• Project/Area Number: 18685011
• Research Category: Grant-in-Aid for Young Scientists (A)
• Allocation Type: Single-year Grants
• Research Field: Synthetic chemistry
• Research Institution: Tohoku University
• Principal Investigator: NAKAMURA Itaru Tohoku University, 大学院・理学研究科, 准教授 (00333899)
• Project Period (FY): 2006 – 2008
• Project Status: Completed (Fiscal Year 2008)
• Budget Amount: ¥30,420,000 (Direct Cost: ¥23,400,000、Indirect Cost: ¥7,020,000); Fiscal Year 2008: ¥6,890,000 (Direct Cost: ¥5,300,000、Indirect Cost: ¥1,590,000); Fiscal Year 2007: ¥6,890,000 (Direct Cost: ¥5,300,000、Indirect Cost: ¥1,590,000); Fiscal Year 2006: ¥16,640,000 (Direct Cost: ¥12,800,000、Indirect Cost: ¥3,840,000)
• Keywords: 反応有機化学 / 骨格転位 / βラクタム / インドール / オレフィン配位子 / ベンゾセレノフェン / 銅触媒 / 金触媒 / 白金触媒 / アミノスルホニル化 / スルホニル転位 / インジウム触媒 / [1,3]転位 / ベンゾチオフェン / 付加反応 / 環化付加反応 / メチレンシクロプロパン / イミン / アゼチジン / 複素環化合物

Research Abstract

金や白金などのπルイス酸触媒によりインドール、ベンゾフラン、ベンゾチオフェンなどの多置換ヘテロ環を効率的に合成する手法を開発した。特に、炭素官能基のみならず、硫黄やケイ素などのヘテロ原子官能基が転位基として作用することを明らかにした。この研究過程において、O-プロパルギルオキシム化合物が銅触媒により極めて有用性の高い多置換ベータラクタム化合物へと骨格転位する新規反応を見出した。

Research Products

• [Journal Article] Five-Bond Cleavage in Copper-Catalyzed Skeletal Rearrangement of O-Propargyl Arylaldoximes to β-Lactam (2009)
  • Author(s): Itaru Nakamura, Toshiharu Araki, Masahiro Terada
  • Journal Title: J. Am. Chem. Soc 131 Pages: 2804-2805
  • Peer Reviewed
• [Journal Article] Stereochemistry Control by Ester Group or Olefin Ligand in Platinum-Catalyzed Carboalkoxylation of 6-(1-Alkoxyethoxy)hex-2-ynoates (2009)
  • Author(s): Itaru Nakamura, Ching Siew Chan, Toshiharu Araki, Masahiro Terada, Yoshinori Yamamoto
  • Journal Title: Adv. Synth. Catal 351 Pages: 1089-1100
  • Peer Reviewed
• [Journal Article] Platinum-Catalyzed Consecutive C-N bond Formation-[1, 3] Shift of Carbamoyl and Ester Groups (2009)
  • Author(s): Itaru Nakamura, Yusuke Sato, Sayaka Konta, Masahiro Terada
  • Journal Title: Tetrahedron Letters 50 Pages: 2075-2077
  • Peer Reviewed
• [Journal Article] Platinum-Catalyzed Dehydroalkoxylation-Cyclization Cascade via N-O Bond Cleavage (2009)
  • Author(s): Itaru Nakamura, Yusuke Sato, Masahiro Terada
  • Journal Title: J. Am. Chem. Soc 131 Pages: 4198-4199
  • Peer Reviewed
• [Journal Article] Pt-Catalyzed Multi-Substituted Benzo[b]selenophene (2009)
  • Author(s): Takuma Sato, Itaru Nakamura, Masahiro Terada
  • Journal Title: Eur. J. Org. Chem Pages: 5509-5509
  • Peer Reviewed
• [Journal Article] Gold-catalyzed consecutive [1, 2] alkyl migration-oxygen transfer reaction of 2-alkynyl-1-tetralones (2009)
  • Author(s): Ching Siew Chan, Toshiharu Araki, Itaru Nakamura, Masahiro Terada
  • Journal Title: Tetrahedron Lett 50 Pages: 216-218
  • Peer Reviewed
• [Journal Article] Palladium-Catalyzed Indolization of N-Aroylbenzotriazoles with Disubstituted Alkynes (2009)
  • Author(s): Itaru Nakamura, Tetsuya Nemoto, Naozumi Shiraiwa, Masahiro Terada
  • Journal Title: Org. Lett 11 Pages: 1055-1058
  • Peer Reviewed
• [Journal Article] Five-Bond Cleavage in Copper-Catalyzed Skeletal Rearrangement of O-Propargyl Arylaldoximes to β-Lactam (2009)
  • Author(s): Itaru Nakamura, Toshiharu Araki, Masahiro Terada
  • Journal Title: Journal of the American Chemical Society 131 Pages: 2804-2805
  • Peer Reviewed
• [Journal Article] Platinum-Catalyzed Dehydroalkoxylation-Cyclization Cascade via N-O Bond Cleavage (2009)
  • Author(s): Itaru Nakamura, Yusuke Sato, Masahiro Terada
  • Journal Title: Journal of the American Chemical Society 131 Pages: 4175-4176
  • Peer Reviewed
• [Journal Article] Pt-Catalyzed Multi-Substituted Benzo[b]selenophene (2009)
  • Author(s): Takuma Sato, Itaru Nakamura, Masahiro Terada
  • Journal Title: European Journal of Organic Chemistry Pages: 5509-5512
  • Peer Reviewed
• [Journal Article] Synthesis of Multisubstituted 2-(Dihydrofuran-2(3H) -ylidene)acetates via Intramolecular Carboalkoxylation by Platinum-Olefin Catalyst System (2008)
  • Author(s): Itaru Nakamura, Ching Siew Chan, Toshiharu Araki, Masahiro Terada, Yoshinori Yamamoto
  • Journal Title: Org. Lett 10 Pages: 309-312
  • Peer Reviewed
• [Journal Article] Chirality Transfer in Gold-Catalyzed Carbothiolation of ortho-Alkynylphenyl 1-Arylethyl Sulfides (2008)
  • Author(s): Itaru Nakamura, Takuma Sato, Masahiro Terada, Yoshinori Yamamoto
  • Journal Title: Org. Lett 10 Pages: 2649-2651
  • Peer Reviewed
• [Journal Article] Synthesis of 3- and 6-Sulfonylindoles from ortho-Alkynyl-N-sulfonylanilines by the Use of Lewis Acidic Transition Metal Catalysts (2008)
  • Author(s): Itaru Nakamura, Uichiro Yamagishi, Dschun Song, Sayaka Konta, Yoshinori Yamamoto
  • Journal Title: Chem. Asian J 3 Pages: 285-295
  • Peer Reviewed
• [Journal Article] Gold- and Indium-Catalyzed Synthesis of 3- and 6-Sulofonylindoles from ortho-Alkynyl-N-Sulufonylanilines. Consecutive C-N and C-S Bond Formation through Intramolecular Aminosulfonylation (2007)
  • Author(s): Itaru Nakamura, Uichiro Yamagishi, Dschun Song, Sayaka Konta, Yoshinori Yamamoto
  • Journal Title: Angew. Chem. Int. Ed 46 Pages: 2284-2287
  • Peer Reviewed
• [Journal Article] Gold-catalyzed cyclization of (ortho-alkynylphenylthio)silanes; intramolecular capture of the vinyl-Au intermediate by the silicon electrophile (2007)
  • Author(s): Itaru Nakamura, Takuma Sato, Masahiro Terada, Yoshinori Yamamoto
  • Journal Title: Org. Lett 9 Pages: 4081-4083
  • Peer Reviewed
• [Journal Article] Synthesis of 1, 2, 3, 4-Tetrasubstituted Pyrroles Derivatives via the Palladium-Catalyzed Reaction of 1, 3-Diketones with Methyleneaziridines (2007)
  • Author(s): Kalum K.A.D.S. Kathriarachchi, Amal I. Siriwardana, Itaru Nakamura, Yoshinori Yamamoto
  • Journal Title: Tetrahedron Lett 48 Pages: 2267-2270
  • Peer Reviewed
• [Journal Article] Synthesis of 2, 3-disubstituted benzofurans and indoles byπ-Lewis acidic transition metal-catalyzed cyclization of ortho-alkynylphenyl O, O- and N, O-acetals (2007)
  • Author(s): Itaru Nakamura, Yuya Mizushima, Uichiro Yamagishi, Yoshinori Yamamoto
  • Journal Title: Tetrahedron 63 Pages: 8670-8676
  • Peer Reviewed
• [Journal Article] Thermally Induced [2+2] Cycloadditions of (Benzyloxymethylene)cyclopropane to Alkylidenemalononitriles (2007)
  • Author(s): Itaru Nakamura, Ryoko Nagata, Tetsuya Nemoto, Masahiro Terada, Yoshinori Yamamoto, Thomas Spath, Armin de Meijere
  • Journal Title: Eur. J. Org. Chem Pages: 4479-4482
  • Peer Reviewed
• [Journal Article] Gold- and Indium-Catalyzed Synthesis of 3- and 6-Sulofonylindoles from ortho-Alkynyl-N-Sulufonylanilines. Consecutive C-N and C-S Bond Formation through Intramolecular Aminosulfonylation (2007)
  • Author(s): Itaru Nakamura, Uichiro Yamagishi, Dschun Song, Sayaka Konta, Yoshinori Yamamoto
  • Journal Title: Angewandte Chemie International Edition 46 Pages: 2284-2287
  • Peer Reviewed
• [Journal Article] Gold-catalyzed cyclization of(ortho-alkynylphenylthio)silanes; intramolecular capture of the vinyl-Au intermediate by the silicon electrophile (2007)
  • Author(s): Itaru Nakamura, Takuma Sato, Masahiro Terada, and Yoshinori Yamamoto
  • Journal Title: Organic Letters 9 Pages: 4081-4083
  • Peer Reviewed
• [Journal Article] Synthesis of 2,3-disubstituted benzofurans and indoles by π-Lewis acidic transition metal-cat alyzed cyclization of ortho-alkynylphenyl O,O- and N,O-acetals (2007)
  • Author(s): Itaru Nakamura, Yuya Mizushima, Uichiro Yamagishi, Yoshinori Yamamoto
  • Journal Title: Tetrahedron 63 Pages: 8670-8676
  • Peer Reviewed
• [Journal Article] Thermally Induced [2+2] Cycloadditions of(Benzyloxymethylene)cyclopropane to Alkylidenemalononitriles (2007)
  • Author(s): Itaru Nakamura, Ryoko Nagata, Tetsuya Nemoto, Masahiro Terada, Yoshinori Yamamoto, Thomas Spath, and Armin de Meijere
  • Journal Title: European Journal of Organic Chemistry Pages: 4479-4482
  • Peer Reviewed
• [Journal Article] Synthesis of 1,2,3,4-Tetrasubstituted Pyrroles Derivatives via the Palladium-Catalyzed Reaction of 1,3-Diketones with Methyleneaziridines (2007)
  • Author(s): Kalum K. A. D. S. Kathriarachchi, Amal I. Siriwardana, Itaru Nakamura, Yoshinori Yamamoto
  • Journal Title: Tetrahedron Letters 48 Pages: 2267-2270
  • Peer Reviewed
• [Journal Article] Gold-Catalyzed Intramolecular Carbothiolation of Alkynes. Synthesis of 2, 3-Disubstituted Benzothiophenes fromα-Alkoxylalkyl (ortho-Alkynyl)phenyl Sulfides (2006)
  • Author(s): Itaru Nakamura, Takuma Sato, Yoshinori Yamamoto
  • Journal Title: Angew. Chem. Int. Ed 45 Pages: 4473-4475
  • Peer Reviewed
• [Journal Article] Palladium-Catalyzed Dimerization of Conjugated Diynes: Synthesis of (E)-1, 2-Divinyldiethynylethenes Having Donor and Acceptor Chromophores at the Terminus of Alkyne (2006)
  • Author(s): Nirmal K. Pahadi, Draxel H. Camacho, Itaru Nakamura, Yoshinori Yamamoto
  • Journal Title: J. Org. Chem 71(3) Pages: 1152-1155
  • Peer Reviewed
• [Journal Article] Thermally Induced and Silver Salt-Catalyzed [2+2] Cycloadditions of Imines to (Alkoxymethylene)cyclopropanes (2006)
  • Author(s): Itaru Nakamura, Tetsuya Nemoto, Yoshinori Yamamoto, Armin de Meijere
  • Journal Title: Angew. Chem. Int. Ed 45 Pages: 5176-5179
  • Peer Reviewed
• [Journal Article] Palladium-Catalyzed Dimerization of Conjugated Diynes : Synthesis of (E)-1,2-Divinyldiethynylethenes Having Donor and Acceptor Chromophores at the Terminus of Alkyne (2006)
  • Author(s): Nirmal K. Pahadi
  • Journal Title: The Journal of Organic Chemistry 71・3 Pages: 1152-1155
• [Journal Article] Gold- Catalyzed Intramolecular Carbothiolation of Alkynes. Synthesis of 2,3-Disubstituted Benzothiophenes from α-Alkoxylalkyl (ortho-Alkynyl)phenyl Sulfides (2006)
  • Author(s): Itaru Nakamura
  • Journal Title: Angewandte Chemie, International Edition 45・27 Pages: 4473-4475
• [Journal Article] Thermally Induced and Silver Salt-Catalyzed [2+2] Cycloadditions of Imines to (Alkoxymethylene)cyclopropanes (2006)
  • Author(s): Itaru Nakamura
  • Journal Title: Angewandte Chemie, International Edition 45・31 Pages: 5176-5179
• [Presentation] 金属触媒を用いた新規医薬(中間体)の合成技術」 (2009)
  • Author(s): 中村達
  • Organizer: 矢野経済研究所"東北テクノアーチ特許技術ご紹介セミナー第1弾「医療・ライフサイエンスの未来」
  • Place of Presentation: 東京
  • Year and Date: 2009-12-02
• [Presentation] π酸性遷移金属触媒による多置換ヘテロ環構築反応の開発 (2009)
  • Author(s): 中村達
  • Organizer: 有機金属若手研究者の会
  • Place of Presentation: 京都
  • Year and Date: 2009-09-08
• [Presentation] 5つの結合の開裂を伴う触媒的骨格転位反応 (2009)
  • Author(s): 中村達・新木利治・寺田眞浩
  • Organizer: 第95回有機合成シンポジウム
  • Place of Presentation: 東京
• [Presentation] Five-Bond Cleavage in Copper-Catalyzed Skeletal Rearrangement of O-Propargyl Arylaldoximes to β-Lactams (2009)
  • Author(s): Itaru Nakamura, Toshiharu Araki, Masahiro Terada
  • Organizer: 15th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS 15)
  • Place of Presentation: Glasgow, Switzerland
• [Presentation] N-O結合の開裂を経由する新規π酸性遷移金属触媒反応 (2009)
  • Author(s): 中村達
  • Organizer: 京都大学グローバルcoe有機若手ワークショップ
  • Place of Presentation: 京都
• [Presentation] 銅触媒による5つの結合の開裂を伴う新規骨格転位反応 (2009)
  • Author(s): 中村達・新木利治・寺田眞浩
  • Organizer: 第56回有機金属化学討論会
  • Place of Presentation: 京都
• [Presentation] n-o結合の開裂を経由する新規π酸性遷移金属触媒反応 (2009)
  • Author(s): 中村達
  • Organizer: 平成21年度化学系学協会東北大会
  • Place of Presentation: 郡山
• [Presentation] 白金触媒によるN-O結合の開裂を伴う脱アルコール環化反応 (2009)
  • Author(s): 中村達・佐藤悠介・寺田眞浩
  • Organizer: 第39回複素環化学討論会
  • Place of Presentation: 柏
• [Presentation] Five-Bond Cleavage in Copper-Catalyzed Skeletal Rearrangement of O-Propargyl Arylaldoximes to β-Lactams (2009)
  • Author(s): Itaru Nakamura
  • Organizer: OMCOS 15
  • Place of Presentation: グラスゴー、英国
• [Presentation] 白金-オレフィン触媒系による分子内カルボアルコキシ化反応 (2007)
  • Author(s): 中村 達
  • Organizer: 第100回触媒討論会
  • Place of Presentation: 北海道大学
  • Year and Date: 2007-09-19
• [Presentation] 白金-オレフィン触媒系による分子内カルボアルコキシ化反応 (2007)
  • Author(s): 中村達・水島祐也・Ching Siew Chan・新木利治・寺田眞浩・山本嘉則
  • Organizer: 第100回触媒討論会
  • Place of Presentation: 札幌
• [Presentation] Gold-and Indium-Catalyzed Synthesis of 3- and 6-Sulfonylindoles from ortho-Alkynyl-N-sulfonylanilines (2007)
  • Author(s): Itaru Nakamura, Uichiro Yamagishi, Dschun Song, Sayaka Konta, Masahiro Terada, and Yoshinori Yamamoto
  • Organizer: RSC conference: 20th International Symposium: Synthesis in Organic Chemistry
  • Place of Presentation: ケンブリッジ大学(イギリス)
• [Presentation] Synthesis of 1,2,3,4-Tetrasubstituted Pyrrole Derivatives via the Palladium-Cataly zed Reaction of 1,3-Diketones with Methyleneaziridines (2007)
  • Author(s): Kalum K. A. D. S. Kathriarachchi, Amal I. Siriwardana, Itaru Nakamura and Yoshinori Yamamoto
  • Organizer: RSC conference: 20th International Symposium: Synthesis in Organic Chemistry
  • Place of Presentation: ケンブリッジ大学(イギリス)
• [Presentation] Gold-and Indium-Catalyzed Synthesis of 3-and 6-Sulfonylindoles from ortho-Alkynyl-N-sulfonylanilines (2007)
  • Author(s): Itaru Nakamura, Uichiro Yamagishi, Dschun Song, Sayaka Konta, Masahiro Terada, and Yoshinori Yamamoto
  • Organizer: 14^<14>IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS 14)
  • Place of Presentation: なら百年会館(奈良)
• [Presentation] 炭素-ヘテロ原子結合の触媒的付加反応による多置換複素芳香環化合物の合成 (2006)
  • Author(s): 中村達・水島祐也・嶋田朋嘉・山岸宇一郎・佐藤太久真・ソンジュン・今田さやか・寺田眞浩・山本嘉則
  • Organizer: 第53回有機金属化学討論会
  • Place of Presentation: 大阪
• [Presentation] Synthesis of Multi-substituted Heteroarenes via Catalytic Carbon-Heteroatom Bond Addition (2006)
  • Author(s): Nakamura, I.; Mizushima, Y.; Yamagishi, U.; Sato, T.; Song, D.; Konta, S.; Terada, M.; Yamamoto, Y
  • Organizer: The Tenth International Kyoto Conference on New Aspects of Organic Chemistry (IKCOC-10)
  • Place of Presentation: Kyoto
• [Remarks]
  • URL: http://www.orgreact.sakura.ne.jp/index.html
• [Remarks]
  • URL: http://www.orgreact.sakura.ne.jp/
• [Patent(Industrial Property Rights)] 新規β-ラクタム合成法 (2009)
  • Inventor(s): 中村達、寺田眞浩、新木利治
  • Industrial Property Rights Holder: 東北大学
  • Industrial Property Number: 2009-191400
  • Filing Date: 2009-08-04
• [Patent(Industrial Property Rights)] 新規β-ラクタム合成法 (2009)
  • Inventor(s): 中村達、寺田眞浩、新木利治
  • Industrial Property Rights Holder: 中村達、寺田眞浩、新木利治
  • Industrial Property Number: 2009-181400
  • Filing Date: 2009-08-04