Asymmetric Synthesis Based on the Generation of Chiral Three-Membered Halonium

• Project/Area Number: 18350023
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Organic chemistry
• Research Institution: Osaka University
• Principal Investigator: MINAKATA Satoshi Osaka University, 大学院・工学研究科, 准教授 (90273599)
• Co-Investigator(Kenkyū-buntansha): 小松 満男 大阪大学, 阿南工業高等専門学校, 校長 (60029197) ; 大平落 洋二 大阪大学, 大学院工学研究科, 助手 (60324810)
• Project Period (FY): 2006 – 2008
• Project Status: Completed (Fiscal Year 2008)
• Budget Amount: ¥16,560,000 (Direct Cost: ¥14,700,000、Indirect Cost: ¥1,860,000); Fiscal Year 2008: ¥4,030,000 (Direct Cost: ¥3,100,000、Indirect Cost: ¥930,000); Fiscal Year 2007: ¥4,030,000 (Direct Cost: ¥3,100,000、Indirect Cost: ¥930,000); Fiscal Year 2006: ¥8,500,000 (Direct Cost: ¥8,500,000)
• Keywords: キラル環状ハロニウム / 不斉合成 / 立体選択性 / 環状ヨードニウム / 光学活性 / キラルヨードニウム / 窒素-ヨウ素結合 / 次亜ヨウ素酸tert-ブチル / N-ヨードスクシンイミド / 二座型キラル分子 / 分子軌道計算 / ビスオキサゾリン

Research Abstract

三員環状のハロニウムイオンは、非常に活性な反応中間体である。アキラルなハロニウムイオンを経由する合成反応は古くから開発されており、数多くの反応が知られているが、キラルなハロニウムイオンの存在はこれまでに知られておらず、新しい不斉合成反応の機軸を生み出すと期待される。本研究では、キラルな三員環状ハロニウムイオンの創製とこれを経由する新しい不斉合成反応の開拓を検討し、光学活性なハロニウムとくにヨードニウム源を設計・合成し、これを活用する不斉誘起を達成した。

Research Products

• [Journal Article] Utilization of N-X Bonds in The Synthesis of N-Heterocycles (2009)
  • Author(s): Satoshi Minakata
  • Journal Title: Acc. Chem. Res. 42 Pages: 1172-1182
  • Peer Reviewed
• [Journal Article] Aziridination of C60 with Simple Amides and Catalytic Rearrangement of the Aziridinofullerenes to Azafulleroids (2009)
  • Author(s): Ryoji Tsuruoka, Toshiki Nagamachi, Yuta Murakami, Mitsuo Komatsu, Satoshi Minakata
  • Journal Title: J. Org. Chem. 74 Pages: 1691-1697
  • Peer Reviewed
• [Journal Article] Organic Reaction on Silica in Water (2009)
  • Author(s): Satoshi Minakata, Mitsuo Komatsu
  • Journal Title: Chem. Rev. 109 Pages: 711-724
  • Peer Reviewed
• [Journal Article] Asymmetric Recognition and Sequential Ring Opening of 2-Substituted-N-Nosylaziridines with (DHQD)2AQN and TMSNu (2009)
  • Author(s): Satoshi Minakata, Yuta Murakami, Masamitsu Satake, Ikumasa Hidaka, Yuriko Okada, Mitsuo Komatsu
  • Journal Title: Org. Biomol. Chem. 7 Pages: 641-643
  • Peer Reviewed
• [Journal Article] Asymmetric Recognition and Sequential Ring Opening of 2-Substituted-N-Nosylaziridines with(DHQD)_2AQN and TMSNu (2009)
  • Author(s): Satoshi Minakata
  • Journal Title: Org.Biomol.Chem. 7 Pages: 641-643
  • Peer Reviewed
• [Journal Article] Organic Reaction on Silica in Water (2009)
  • Author(s): Satoshi Minakata
  • Journal Title: Chem.Rev. 109 Pages: 711-724
  • Peer Reviewed
• [Journal Article] Aziridination of C_<60> with Simple Amides and Catalytic Rearrangement of the Aziridinofullerenes to Azafulleroids (2009)
  • Author(s): Satoshi Minakata
  • Journal Title: J.Org.Chem. 74 Pages: 1691-1697
  • Peer Reviewed
• [Journal Article] Utilization of N-X Bonds in The Synthesis of N-Heterocycles (2009)
  • Author(s): Satoshi Minakata
  • Journal Title: Acc.Chem.Res. 42 Pages: 1172-1182
  • Peer Reviewed
• [Journal Article] Catalytic Aziridination of Electron-Deficient Olefins with N-Chloro-N-sodiocarbamate and Application of This Novel Method to Asymmetric Synthesis (2008)
  • Author(s): Satoshi Minakata, Yuta Murakami, Ryoji Tsuruoka, Shinsuke Kitanaka, Mitsuo Komatsu
  • Journal Title: Chem. Commun. Pages: 6363-6365
  • Peer Reviewed
• [Journal Article] Inclusion of C60 into MCM-41 by Solvophobic Nature (2008)
  • Author(s): Satoshi Minakata, Ryoji Tsuruoka, Mitsuo Komatsu
  • Journal Title: J. Am. Chem. Soc. 130 Pages: 1536-1537
  • Peer Reviewed
• [Journal Article] Novel Fluorescent Aluminum Complexes Based on N-Hydroxy-3, 6-diaryl-4-phenyl-2-pyridone Ligands (2008)
  • Author(s): Satoshi Minakata, Hiroshi Inada, Mitsuo Komatsu, Hirotake Kajii, Yutaka Ohmori, Manabu Tsumura, Kiyoyuki Namura
  • Journal Title: Chem. Lett. Pages: 248-249
  • NAID: 10021077976
  • Peer Reviewed
• [Journal Article] Ionic Introduction of an N1 Unit to C60 and Unique Rearrangement of Aziridinofullerene (2008)
  • Author(s): Satoshi Minakata, Ryoji Tsuruoka, Toshiki Nagamachi, Mitsuo Komatsu
  • Journal Title: Chem. Commun. Pages: 323-325
  • Peer Reviewed
• [Journal Article] Catalytic Aziridination of Electron-Deficient Olefins with N-Chloro-N-sodiocarbamate and Application of This Novel Method to Asymmetric Synthesis (2008)
  • Author(s): Satoshi Minakata
  • Journal Title: Chem.Commun. Pages: 6363-6365
  • Peer Reviewed
• [Journal Article] Ionic Introduction of an N_1 Unit to C_<60> and Unique Rearrangement of Aziridinofullerene (2008)
  • Author(s): Satoshi Minakata
  • Journal Title: Chem. Commun. Pages: 323-325
  • Peer Reviewed
• [Journal Article] Novel Fluorescent Aluminum Complexes Based on N-Hydroxy-3, 6-diaryl-4-phenyl-2-pyridone Ligands (2008)
  • Author(s): Satoshi Minakata
  • Journal Title: Chem Lett. Pages: 248-249
  • NAID: 10021077976
  • Peer Reviewed
• [Journal Article] Inclusion of C_<60> into MCM-41 by Solvophobic Nature (2008)
  • Author(s): Satoshi Minakata
  • Journal Title: J. Am. Chem. Soc. Pages: 1536-1537
  • Peer Reviewed
• [Journal Article] (2007)
  • Author(s): Satoshi Minakata, Yoshinobu Morino, Toshihiro Ide, Yoji Oderaotoshi, Mitsuo Komatsu
  • Journal Title: Chem. Commun. Pages: 3279-3281
  • Peer Reviewed
• [Journal Article] Synthesis and Spectroscopic Properties of New Fluorescent 3, 6-Diaryl-4-phenyl-2-pyridone Derivatives (2007)
  • Author(s): Satoshi Minakata, Shouta Moriwaki, Hiroshi Inada, Mitsuo Komatsu, Kajii Hirotake, Yutaka Ohmori, Manabu Tsumura, Kiyoyuki Namura
  • Journal Title: Chem. Lett. Pages: 1014-1015
  • NAID: 10019744180
  • Peer Reviewed
• [Journal Article] Three-Component Coupling of a Silylene, Aldehydes and Electron-Deficient Acetylenes via 1 (2007)
  • Author(s): Satoshi Minakata, Seishi Ohashi, Yusuke Amano, Yoji Oderaotoshi, Mitsuo Komatsu
  • Journal Title: 3-Dipolar Cycloaddition Synthesis Pages: 2481-2484
  • Peer Reviewed
• [Journal Article] Three-Component Coupling of a Silylene, Aldehydes and Electron-Deficient Acetylenes via 1, 3-bipolar Cycloaddition (2007)
  • Author(s): Satoshi Minakata
  • Journal Title: Synthesis Pages: 2481-2484
  • Peer Reviewed
• [Journal Article] Synthesis and Spectroscopic Properties of New Fluorescent 3, 6-Diaryl-4-phenyl-2-pyridone Derivatives (2007)
  • Author(s): Satoshi Minakata
  • Journal Title: Chem Lett. Pages: 1014-1015
  • NAID: 10019744180
  • Peer Reviewed
• [Journal Article] Direct Synthesis of Oxazolines from Olefins and Amides Using tert-BuOI (2007)
  • Author(s): Satoshi Minakata
  • Journal Title: Chem. Commun. Pages: 3279-3281
  • Peer Reviewed
• [Journal Article] SynthesOctahydropyrrolo[3, 2-c]pyridine Derivatives by the Catalytic Asymmetric Intramolecular Cycloaddition of Azomethine Ylides (2006)
  • Author(s): Yoji Oderaotoshi, Hiroyuki Miyata, Satoshi Minakata, Mitsuo Komatsu
  • Journal Title: Heterocycles 68 Pages: 2465-2469
  • Peer Reviewed
• [Journal Article] Ring Opening and Expansion of Aziridines in a Silica-Water Reaction Medium (2006)
  • Author(s): Satoshi Minakata, Takahiro Hotta, Yoji Oderaotoshi, Mitsuo Komatsu
  • Journal Title: J. Org. Chem. 71 Pages: 7471-7472
  • Peer Reviewed
• [Journal Article] Electrophilic Cyclization of N-Alkenylamides Using a Chloramine-T/I2 System (2006)
  • Author(s): Yoshinobu Morino, Ikumasa Hidaka, Yoji Oderaotoshi, Mitsuo Komatsu, Satoshi Minakata
  • Journal Title: Tetrahedron 62 Pages: 12247-12251
  • Peer Reviewed
• [Journal Article] 1, 6-Stannatropic Strategy: Effective Generation and Cyclization of 1, 5-Dipoles from o-Stannylmethylated Thioanilides or Phenyl Isothiocyanates (2006)
  • Author(s): Satoshi Minakata, Yukihiro Kasano, Hirofumi Ota, Yoji Oderaotoshi, Mitsuo Komatsu
  • Journal Title: Org. Lett. 8 Pages: 3693-3695
  • Peer Reviewed
• [Journal Article] Practical and Convenient Synthesis of N-Heterocycles: Stereoselective Cyclization of N-Alkenylamides with t-BuOI under Neutral Conditions (2006)
  • Author(s): Satoshi Minakata, Yoshinobu Morino, Yoji Oderaotoshi, Mitsuo Komatsu
  • Journal Title: Org. Lett. 8 Pages: 3335-3337
  • Peer Reviewed
• [Journal Article] Novel Aziridination of Olefins: Direct Synthesis from Sulfonamides Using t-BuOI (2006)
  • Author(s): Satoshi Minakata, Yoshinobu Morino, Yoji Oderaotoshi, Mitsuo Komatsu
  • Journal Title: Chem. Commun. Pages: 3337-3339
  • Peer Reviewed
• [Journal Article] Aziridination of Olefines : Direct Synthesis from Sulfonamides Using t-BuOI (2006)
  • Author(s): Satoshi Minakata
  • Journal Title: Chem. Commun. 31 Pages: 3337-3339
• [Journal Article] Practical and Convenient Synthesis of N-Heterocycles : Stereoselective Cyclization of N-Alkenylamides with t-BuOI under Neutral Conditions (2006)
  • Author(s): Satoshi Minakata
  • Journal Title: Org. Lett. 8・15 Pages: 3335-3337
• [Journal Article] 1,6-Stannatropic Strategy : Effective Generation and Cyclization of 1,5-Dipoles from o-Stannylmethylated Thioanilides or Phenyl Isothiocyanates (2006)
  • Author(s): Satoshi Minakata
  • Journal Title: Org. Lett. 8・17 Pages: 3693-3695
• [Journal Article] Electrophilic Cyclization of N-Alkyenylamides using a Chlororamine T/I_2 System (2006)
  • Author(s): Satoshi Minakata
  • Journal Title: Tetrahedron 62・52 Pages: 12247-12251
• [Journal Article] Ring Opening and Exapnsion of Aziridines in a Silica-Water Reaction medium (2006)
  • Author(s): Satoshi Minakata
  • Journal Title: J. Org. Chem 71・19 Pages: 7471-7472
• [Journal Article] Synthesis of Octahydropyrrolo [3,2-c] pyridine Derivatives by the Catalytic Asymmetric Intramolecular Cycloaddition of Azomethine Ylides (2006)
  • Author(s): Satoshi Minakata
  • Journal Title: Heterocycles 68・12 Pages: 2465-2469
  • NAID: 40015181984
• [Presentation] t-BuOIを用いる不飽和アルコールへの常圧二酸化炭素固定 (2008)
  • Author(s): 南方聖司
  • Organizer: 第11回ヨウ素学会シンポジウム
  • Place of Presentation: 千葉大学
  • Year and Date: 2008-11-07
• [Presentation] t-BuOIを用いるアリルアルコールとCO2からの環状カーボネート合成 (2008)
  • Author(s): 南方聖司
  • Organizer: 日本化学会第88春季年会
  • Place of Presentation: 立教大学
  • Year and Date: 2008-03-27
• [Presentation] t-BuOIを用いるアリルアルコールとCO_2からの環状カーボネート合成 (2008)
  • Author(s): 南方聖司
  • Organizer: 日本化学会第88春季年会
  • Place of Presentation: 立教大学
  • Year and Date: 2008-03-27
• [Presentation] N・ハロアミド類による電子不足オレフィンの触媒的アジリジン化とその不斉合成への応用 (2008)
  • Author(s): 南方聖司
  • Organizer: 第35回有機典型元素化学討論会
  • Place of Presentation: 首都大学東京
• [Presentation] N・クロロ・N・ソジオカルバマートを窒素源とする電子不足オレフィンの触媒的アジリジン化とその不斉合成への応用 (2008)
  • Author(s): 南方聖司
  • Organizer: 第38回複素環化学討論会
  • Place of Presentation: 広島県民文化センターふくやま
• [Presentation] N-クロロ-N-ソジオカルバマートを窒素源とする電子不足オレフィンの触媒的アジリジン化とその不斉合成への応用 (2008)
  • Author(s): 南方聖司
  • Organizer: 第38回複素環化学討論会
  • Place of Presentation: 広島県民文化センターふくやま
• [Presentation] N-ハロアミド類による電子不足オレフィンの触媒的アジリジン化とその不斉合成への応用 (2008)
  • Author(s): 南方聖司
  • Organizer: 第35回有機典型元素化学討論会
  • Place of Presentation: 首都大学東京
• [Presentation] t-BuOIを活用するアミドとオレフィンからの新規オキサゾリン合成 (2007)
  • Author(s): 南方聖司
  • Organizer: 第10回ヨウ素学会シンポジウム
  • Place of Presentation: 千葉大学
  • Year and Date: 2007-11-16