Precise Organic Synthesis Using Organic Superbase

• Project/Area Number: 19390002
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Chemical pharmacy
• Research Institution: Tohoku University
• Principal Investigator: KONDO Yoshinori 東北大学, 大学院・薬学研究科, 教授 (90162122)
• Project Period (FY): 2007 – 2010
• Project Status: Completed (Fiscal Year 2010)
• Budget Amount: ¥19,240,000 (Direct Cost: ¥14,800,000、Indirect Cost: ¥4,440,000); Fiscal Year 2010: ¥2,730,000 (Direct Cost: ¥2,100,000、Indirect Cost: ¥630,000); Fiscal Year 2009: ¥3,250,000 (Direct Cost: ¥2,500,000、Indirect Cost: ¥750,000); Fiscal Year 2008: ¥3,250,000 (Direct Cost: ¥2,500,000、Indirect Cost: ¥750,000); Fiscal Year 2007: ¥10,010,000 (Direct Cost: ¥7,700,000、Indirect Cost: ¥2,310,000)
• Keywords: 合成化学 / フォスファゼン / 有機超強塩基 / 触媒反応 / 有機ケイ素 / 有機亜鉛 / 脱プロトン / 芳香環 / 複素環 / 有機合成 / 触媒 / 有機金属 / 結合活性化 / 炭素アニオン / 選択性

Research Abstract

Selective transformations were developed using phosphazene bases and the reactions were further optimized toward phosphazene catalyzed reactions. First, deprotonation of aromatic ring proton was achieved using phosphazene P4 base and also arylsilanes were activated by the catalytic use of the P4 base. Organozinc compounds were found to be activated by phosphazene base and the halogen-zinc exchange reaction of functionalized aryl halides was successfully accomplished in the presence of P4 catalyst.

Research Products

• [Journal Article] Functionalization of Heteroaromatic N-Oxides Using Organic Superbase Catalyst (2011)
  • Author(s): Yuta Araki, Koji Kobayashi, Misato Yonemoto, Yoshinori Kondo
  • Journal Title: Org. Biomol. Chem. Volume: 9 Pages: 78-80
  • Peer Reviewed
• [Journal Article] Functionalization of heteroaromatic N-oxide using organic superbase catalyst (2011)
  • Author(s): Y.Araki, K.Kobayashi, M.Yonemoto, Y.Kondo
  • Journal Title: Organic & Biomolecular Chemistry Volume: 9 Pages: 78-80
  • Peer Reviewed
• [Journal Article] Metal-free Deprotonative Functionalization of Heteroaromatics Using Organic Superbase Catalyst (2010)
  • Author(s): Yutaro Hirono, Koji Kobayashi, Misato Yonemoto, Yoshinori Kondo
  • Journal Title: Chem. Commun. Volume: 46 Pages: 7623-7624
  • Peer Reviewed
• [Journal Article] Generation of Arylzinc Reagents Through an Iodine-Zinc Exchange Reaction Promoted by a Non-metallic Organic Superbase (2010)
  • Author(s): Hiroshi Naka, Keisuke Ito, Masahiro Ueno, Koji Kobayashi, Yoshinori Kondo
  • Journal Title: New J. Chem. Volume: 34 Pages: 1700-1706
  • Peer Reviewed
• [Journal Article] Metal-free deprotonative functionalization of heteroaromatics using organic superbase catalyst (2010)
  • Author(s): Y.Hirono, K.Kobayashi, M.Yonemoto, Y.Kondo
  • Journal Title: Chemical Communications Volume: 46 Pages: 7623-7624
  • Peer Reviewed
• [Journal Article] Generation of arylzinc reagents through iodine-zinc exchange reaction promoted by a non-metallic organic superbase (2010)
  • Author(s): H.Naka, K.Ito, M.Ueno, K.Kobayashi, Y.Kondo
  • Journal Title: New Journal of Chemistry Volume: 34 Pages: 1700-1706
  • Peer Reviewed
• [Journal Article] 0価パラジウム触媒と有機ホウ素試薬を用いた分子内求電子剤を有するアルキン・アレンの付加・環化反応 (2010)
  • Author(s): 塚本裕一、根東義則
  • Journal Title: 有機合成化学協会誌 68 Pages: 143-152
  • NAID: 10026867963
  • Peer Reviewed
• [Journal Article] SN2' Reaction of Organozinc Reagents Activated by Catalytic tBu-P4 Base in the presence of LiCl (2009)
  • Author(s): Koji Kobayashi, Masahiro Ueno, Hiroshi Naka, Yoshinori Kondo
  • Journal Title: Chem. Eur. J. Volume: 15 Pages: 9805-9809
  • Peer Reviewed
• [Journal Article] Transition Metal Free Carboxylation of Organozinc Reagents Using CO2 in DMF Solvent (2009)
  • Author(s): Koji Kobayashi, Yoshinori Kondo
  • Journal Title: Org. Lett. Volume: 11 Pages: 2035-2037
  • Peer Reviewed
• [Journal Article] S_N2' Reaction of Organozinc Reagents Activated by Catalytic tBu-P4 Base in the presence of LiCl (2009)
  • Author(s): Koji Kobayashi, Masahiro Ueno, Hiroshi Naka, Yoshinori Kondo
  • Journal Title: Chem.Eur.J. 15 Pages: 9805-9809
  • Peer Reviewed
• [Journal Article] Transition Metal Free Carboxylation of Organozinc Reagents Using CO_2 in DMF Solvent (2009)
  • Author(s): Koji Kobayashi, Yoshinori Kondo
  • Journal Title: Org.Lett. 11 Pages: 2035-2037
  • Peer Reviewed
• [Journal Article] S_N2' Reaction of Organozinc Reagents Activated by Catalytic tBu-P4 Base in the presence of LiCl (2009)
  • Author(s): K.Kobayashi, M.Ueno, H.Naka, Y.Kondo
  • Journal Title: Chem.Eur.J. 15 Pages: 9805-9809
  • Peer Reviewed
• [Journal Article] Transition Metal Free Carboxylation of Organozinc Reagents Using CO_2 in DMF Solvent (2009)
  • Author(s): K.Kobayashi, Y.Kondo
  • Journal Title: Org.Lett. 11 Pages: 2035-2037
  • Peer Reviewed
• [Journal Article] Activation of organozinc reagents with t-Bu-P4 base for transition metal-free catalytic SN2' reaction (2008)
  • Author(s): Koji Kobayashi, Masahiro Ueno, Hiroshi Naka, Yoshinori Kondo
  • Journal Title: Chem. Commun. Pages: 3780-3782
  • Peer Reviewed
• [Journal Article] Organozinc Reagents in DMSO Solvent : Remarkable Promotion of SN2' Reaction for Allene Synthesis (2008)
  • Author(s): Koji Kobayashi, Hiroshi Naka, Andrew E. H. Wheatley, Yoshinori Kondo
  • Journal Title: Org. Lett. Volume: 10 Pages: 3375-3377
  • Peer Reviewed
• [Journal Article] Chiral bisphosphazides as dual basic enantioselective catalysts (2008)
  • Author(s): Hiroshi Naka, Nobuhiko Kanase, Masahiro Ueno, Yoshinori Kondo
  • Journal Title: Chem. Eur. J. Volume: 14 Pages: 5267-5274
  • Peer Reviewed
• [Journal Article] Activation of organozinc reagents with t-Bu-P4 base for transition metal-free catalytic SN2' reaction (2008)
  • Author(s): Koji Kobayashi, Masahiro Ueno, Hiroshi Naka, Yoshinori Kondo
  • Journal Title: Chem.Commun. Pages: 3780-3782
  • Peer Reviewed
• [Journal Article] On the Kinetic and Thermodynamic Reactivity of Lithium Di(alkyl)amidozincate Bases in Directed Ortho Metalation (2007)
  • Author(s): Kondo, Y; Morey, J. V; Morgan, J. C; Naka, H; Nobuto, D; Raithby, P. R; Uchiyama, M. Wheatley, A. E. H.
  • Journal Title: J. Am. Chem. Soc. 129 Pages: 12734-12738
  • Peer Reviewed
• [Journal Article] Deprotonative Metalation Using Ate Compounds: Synergy, Synthesis, and Structural Building (2007)
  • Author(s): Mulvey, R. E.; Mongin, F. Uchiyama, M.; Kondo, Y.
  • Journal Title: Angew. Chem. Int. Ed. 46 Pages: 3802-3824
  • Peer Reviewed
• [Journal Article] Synthesis of dictyomedins using phosphazene base catalyzed diaryl ether formation (2007)
  • Author(s): Ebisawa, M.; Ueno, M. Oshima, Y.; Kondo, Y.
  • Journal Title: Tetrahedron Letters 48 Pages: 8918-8921
  • Peer Reviewed
• [Presentation] 有機触媒プロセスによる新規脱プロトン化-修飾反応 (2010)
  • Author(s): 米本みさと、荒木勇太、廣野佑太郎、小林耕士、根東義則
  • Organizer: 第36回反応と合成の進歩シンポジウム
  • Place of Presentation: 名古屋
  • Year and Date: 2010-11-01
• [Presentation] 有機触媒プロセスによる芳香環上C-H結合の直接的変換反応 (2010)
  • Author(s): 廣野佑太郎、米本みさと、小林耕士、根東義則
  • Organizer: 第38回複素環化学討論会
  • Place of Presentation: 仙台
  • Year and Date: 2010-10-14
• [Presentation] フォスファゼン塩基触媒を用いる芳香複素環N-オキシドの脱プロトン-修飾反応 (2010)
  • Author(s): 荒木勇太、小林耕士、米本みさと、根東義則
  • Organizer: 日本薬学会第130年会
  • Place of Presentation: 岡山
  • Year and Date: 2010-03-28
• [Presentation] 有機超強塩基を触媒としたヘテロ環化合物の脱プロトン化修飾反応 (2009)
  • Author(s): 廣野佑太郎、小林耕士、米本みさと、根東義則
  • Organizer: 第35回反応と合成の進歩シンポジウム
  • Place of Presentation: 金沢
  • Year and Date: 2009-11-16
• [Presentation] 有機超強塩基を触媒としたヘテロ環化合物の脱プロトン化修飾反応 (2009)
  • Author(s): 廣野佑太郎, 小林耕士, 米本みさと, 根東義則
  • Organizer: 第35回反応と合成の進歩シンポジウム
  • Place of Presentation: 日、金沢
  • Year and Date: 2009-11-16
• [Presentation] 有機超強塩基触媒を用いる選択的分子変換反応 (2009)
  • Author(s): 根東義則
  • Organizer: 平成21年度化学系学協会東北大会
  • Place of Presentation: 郡山
  • Year and Date: 2009-09-21
• [Presentation] Selective Transformation Using Organic Superbase (2009)
  • Author(s): Y.Kondo
  • Organizer: France-England Interreg IVA Programme
  • Place of Presentation: Forges les Eaux Normandy, France
  • Year and Date: 2009-07-02
• [Presentation] Selective Transformation Using Organic Superbase (2009)
  • Author(s): Yoshinori Kondo
  • Organizer: France . England Interreg IVA Programme, Forges les Eaux, Normandy
  • Place of Presentation: France
• [Presentation] Selective Transformation Using Organic Superbase (2009)
  • Author(s): Yoshinori Kondo
  • Organizer: France-England Interreg IVA Programme, Forges les Eaux
  • Place of Presentation: Normandy, France
• [Presentation] 有機超強塩基触媒を用いる芳香複素環のハロゲン-亜鉛交換反応 (2008)
  • Author(s): 伊藤慶祐、中寛史、根東義則
  • Organizer: 第38回複素環化学討論会
  • Place of Presentation: 福山
  • Year and Date: 2008-11-22
• [Presentation] フォスファゼン塩基を用いた位置選択的ピロール誘導体合成法の開発 (2007)
  • Author(s): 小関大輝、中寛史、根東義則
  • Organizer: 第37回複素環化学討論会
  • Place of Presentation: 長野市(長野市若里市民文化ホール)
  • Year and Date: 2007-10-19
• [Book] Phosphazene : Preparation, Reaction and Catalytic Role, Yoshinori Kondo in"Superbases for Organic Synthesis" (2009)
  • Author(s): Yoshinori Kondo
  • Publisher: Wiley
• [Book] 有機超強塩基を用いる変換反応、「進化を続ける有機触媒」、化学フロンティア (2009)
  • Author(s): 根東義則
  • Publisher: 化学同人
• [Book] Superbases for Organic Synthesis(ed. Tsutomu Ishikawa, Phosphazene : Preparation, Reaction and Catalytic Role) (2009)
  • Author(s): Yoshinori Kondo
  • Publisher: Wiley
• [Book] Phosphazene : Preparation, Reaction and Catalytic Role, in"Superbases for Organic Synthesis" (2009)
  • Author(s): Y.Kondo
  • Total Pages: 40
  • Publisher: Wiley
• [Book] Phosphazene : Preparation, Reaction and Catalytic Role, in "Superbases for Organic Synthesis" (2009)
  • Author(s): Y.Kondo
  • Total Pages: 40
  • Publisher: Wiley
• [Book] 有機超強塩基触媒を用いる分子変換反応(有機分子触媒の新展開、柴崎正勝監修) (2007)
  • Author(s): 根東 義則
  • Publisher: シーエムシー出版
• [Remarks]
  • URL: http://www.pharm.tohoku.ac.jp/~henkan/lab/henkan_top.html
• [Remarks]
  • URL: http://www.pharm.tohoku.ac.jp/~henkan/lab/henkan_top.html
• [Remarks]
  • URL: http://www.pharm.tohoku.ac.jp/~henkan/lab/publications_lab.html
• [Remarks]
  • URL: http://www.pharm.tohoku.ac.jp/~henkan/lab/publications_lab.html
• [Remarks]
  • URL: http://www.pharm.tohoku.ac.jp/~henkan/lab/publications_lab.html
• [Patent(Industrial Property Rights)] 高熱安定性を有する機能性フォスファジド (2008)
  • Inventor(s): 根東義則、中寛史、下哲也
  • Industrial Property Rights Holder: 東北大学
  • Industrial Property Number: 2008-193767
  • Acquisition Date: 2008-07-28
• [Patent(Industrial Property Rights)] 高熱安定性を有する機能性フォスファジド (2008)
  • Inventor(s): 根東義則, 中寛史, 下哲也
  • Industrial Property Rights Holder: 東北大学
  • Industrial Property Number: 2008-193767
  • Filing Date: 2008-07-28