Total Synthesis of Biologically Active Compounds Based on the the Cascade-Type Sigmatropic Rearrangements

• Project/Area Number: 20350021
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Organic chemistry
• Research Institution: Keio University
• Principal Investigator: CHIDA Noritaka 慶應義塾大学, 理工学部, 教授 (50197612)
• Project Period (FY): 2008 – 2011
• Project Status: Completed (Fiscal Year 2011)
• Budget Amount: ¥15,210,000 (Direct Cost: ¥11,700,000、Indirect Cost: ¥3,510,000); Fiscal Year 2011: ¥2,860,000 (Direct Cost: ¥2,200,000、Indirect Cost: ¥660,000); Fiscal Year 2010: ¥2,860,000 (Direct Cost: ¥2,200,000、Indirect Cost: ¥660,000); Fiscal Year 2009: ¥2,860,000 (Direct Cost: ¥2,200,000、Indirect Cost: ¥660,000); Fiscal Year 2008: ¥6,630,000 (Direct Cost: ¥5,100,000、Indirect Cost: ¥1,530,000)
• Keywords: シグマトロピー転位 / Claisen転位 / Overman転位 / カスケード型転位 / モルヒネ / アゲラスタチンA / カイニン酸 / ブロッソネチン / アクロメリン酸 / オルトアミド型転位 / カスケード型反応 / 生物活性物質 / 全合成 / 環状オルトアミド / ブロッソネチンF / 連続Overman転位 / A-315675 / 連続Claisen転位

Research Abstract

Development of the cascade-type sigmatropic rearrangements of chiral allylic vicinal diol compounds which generates new C-C or C-N bonds via chirality transfer of C-O bonds of the substrate has been investigated. Biologically active compounds such as morphine and agelastatin A were successfully synthesized using the cascade-type Claisen and Overman rearrangements. The orthoamide-type Claisen and Overman rearrangements, which required no protecting group manipulation, were also developed. Based on the orthoamide-type rearrangement, effective total syntheses of kainic acid and broussonetine F were achieved.

Research Products

• [Journal Article] Direct Chemoselective Allylation of Inert Amide Carbonyls (2012)
  • Author(s): Yukiko Oda
  • Journal Title: Organic Letters Volume: 14 Issue: 3 Pages: 950-953
  • DOI: 10.1021/ol3000316
  • Peer Reviewed
• [Journal Article] Total Synthesis of Broussonetine F : The Orthoamide Overman Rearrangement of an Allylic Diol (2011)
  • Author(s): Naoto Hama, Toshihiko Aoki, Shohei Miwa, Miki Yamazaki, Takaaki Sato, Noritaka Chida
  • Journal Title: Organic Letters Volume: 13 Pages: 616-619
  • Peer Reviewed
• [Journal Article] Total Synthesis of Broussonetine F : The Orthoamide Overman Rearraangement of an Allylic Diol (2011)
  • Author(s): Naoto Hama, Toshihiko Aoki, Shohei Miwa, Miki Yamazaki, Takaaki Sato, Noritaka Chida
  • Journal Title: Organic Letters 13 Pages: 616-619
  • Peer Reviewed
• [Journal Article] Total Synthesis of (-)-Salinosporamide A (2011)
  • Author(s): Yuji Kaiya
  • Journal Title: Chemistry an Asian Journal Volume: 6 Pages: 209-219
  • Peer Reviewed
• [Journal Article] Novel Sequential Sigmatropic Rearrangements of Allylic Diols : Application to the Total Synthesis of (-)-Kainic Acid (2010)
  • Author(s): Katsunori Kitamoto, Mana Sampei, Yasuaki Nakayama, Takaaki Sato, Noritaka Chida
  • Journal Title: Organic Letters Volume: 12 Pages: 5756-5759
  • Peer Reviewed
• [Journal Article] Novel Sequential Sigmatropic Rearrangements of Allylic Diols : Application to the Total Synthesis of (-)-Kainic Acid (2010)
  • Author(s): Katsunori Kitamoto, Mana Sampei, Yasuaki Nakayama, Takaaki Sato, Noritaka Chida
  • Journal Title: Organic Letters 12 Pages: 5756-5759
  • Peer Reviewed
• [Journal Article] Novel Sequential Sigmatoropic Rearrangements of Allylic Diols : Application to the Total Synthesis of (-)-Kainic Acid (2010)
  • Author(s): Katsunori Kitamoto
  • Journal Title: Organic Letters Volume: 12 Pages: 5756-5759
  • Peer Reviewed
• [Journal Article] Total Synthesis of (-)-Agelastatin A : The Application of a Sequential Sigmatropic Rearrangement (2009)
  • Author(s): Naoto Hama, Tomoki Matsuda, Takaaki Sato, Noritaka Chida
  • Journal Title: Organic Letters Volume: 11 Pages: 2687-2690
  • Peer Reviewed
• [Journal Article] (2009)
  • Author(s): Naoto Hama, Tomoki Matsuda, Takaaki Sato, Noritaka Chida
  • Journal Title: Organic Letters 11 Pages: 2687-2690
  • Peer Reviewed
• [Journal Article] Total synthesis of(-)-agelastatin A : the application of a sequential sigmatropic rearrangement (2009)
  • Author(s): Naoto Hama
  • Journal Title: Organic Letters 11 Pages: 2687-2690
  • Peer Reviewed
• [Journal Article] Formal synthesis of salinosporamide A starting from D-glucose (2009)
  • Author(s): Takayuki Momose
  • Journal Title: Synthesis Pages: 2983-2991
  • Peer Reviewed
• [Journal Article] Total synthesis of mycestericin A and its 14-epimer (2009)
  • Author(s): Hiroyoshi Yamanaka
  • Journal Title: Tetrahedron 65 Pages: 9188-9201
  • Peer Reviewed
• [Journal Article] Total Synthesis of A-315675 Based on the Cascade Overman Rearrangement (2008)
  • Author(s): Takayuki Momose, Naoto Hama, Chiharu Higashino, Hideyuki Sato, Noritaka Chida
  • Journal Title: Tetrahedron Letters Volume: 49 Pages: 1376-1379
  • Peer Reviewed
• [Journal Article] Formal Synthesis of (-)-Morphine from D-Glucal Based on the Cascade Claisen Rearrangement (2008)
  • Author(s): Hiroki Tanimoto, Ryosuke Saito, Noritaka Chida
  • Journal Title: Tetrahedron Letters Volume: 49 Pages: 358-362
  • Peer Reviewed
• [Journal Article] Total Synthesis of A-315675 Based on the Cascade Overman Rearrangement (2008)
  • Author(s): Takayuki Momose, Naoto Hama, Chiharu Higashino, Hideyuki Sato, Noritaka Chida
  • Journal Title: Tetrahedron Letters 49 Pages: 1376-1379
  • Peer Reviewed
• [Journal Article] Formal Synthesis of (-)-Morphine from D-Glucal Based on the Cascade Claisen Rearrangement (2008)
  • Author(s): Hiroki Tanimoto, Ryosuke Saito, Noritaka Chida
  • Journal Title: Tetrahedron Letters 49 Pages: 358-362
  • Peer Reviewed
• [Journal Article] Formal Synthesis (-)-Morphine from D-Glucal Based on the Cascade Claisen Rearrangement (2008)
  • Author(s): Hiroki Tanimoto
  • Journal Title: Tetrahedron Letters 49 Pages: 358-362
  • Peer Reviewed
• [Journal Article] Total Synthesis of A-315675 Based on the Cascade Overman Rearrangement (2008)
  • Author(s): Takayuki Momose
  • Journal Title: Tetrahedron Letters 49 Pages: 1376-1379
  • Peer Reviewed
• [Presentation] 光学活性なアリルジオールに対する連続的シグマトロピー転位 (2011)
  • Author(s): 中山泰彰, 北元克典, 三瓶真菜, 佐藤隆章, 千田憲孝
  • Organizer: 第55回香料・テルペンおよび精油化学に関する討論会
  • Place of Presentation: 筑波大学
  • Year and Date: 2011-11-19
• [Presentation] 連続的シグマトロピー転位の開発とカイノイド類全合成への応用 (2011)
  • Author(s): 北元克典, 三瓶真菜, 中山泰彰, 市來政人, 佐藤隆章, 千田憲孝
  • Organizer: 第53回天然有機化合物討論会
  • Place of Presentation: 大阪国際交流センター
  • Year and Date: 2011-09-28
• [Presentation] Broussonetine Fの全合成 (2011)
  • Author(s): 濱直人, 三輪祥平, 山崎美貴, 佐藤隆章, 千田憲孝
  • Organizer: 日本化学会第91春季年会
  • Place of Presentation: 神奈川大学
  • Year and Date: 2011-03-29
• [Presentation] ワンポット連続反応を利用した生物活性アルカロイドの合成研究 (2010)
  • Author(s): 千田憲孝
  • Organizer: 日本化学会第4回関東支部大会
  • Place of Presentation: 筑波大学
  • Year and Date: 2010-08-30
• [Presentation] ワンポット連続反応を利用した生物活性アルカロイドの合成研究 (2010)
  • Author(s): 千田憲孝
  • Organizer: 日本化学会第4回関東支部大会
  • Place of Presentation: 筑波大学(依頼講演)
  • Year and Date: 2010-08-30
• [Presentation] Total Synthesis of Biologically Active Alkaloids Based on the Cascade Sigmatropic Rearrangement (2010)
  • Author(s): Noritaka Chida
  • Organizer: The 11th Florida Heterocyclic and Synthetic Conference
  • Place of Presentation: フロリダ大学(米国)
  • Year and Date: 2010-03-09
• [Presentation] Total Synthesis of Biologically Active Alkaloids Based on the Cascade Sigmatropic Rearrangement (2010)
  • Author(s): Noritaka Chida
  • Organizer: The 11th Florida Heterocyclic and Synthetic Conference
  • Place of Presentation: フロリダ大学(米国)(招待講演)
  • Year and Date: 2010-03-09
• [Presentation] Total synthesis of biologically active alkaloids based on the cascade sigmatropic rearrangement (2010)
  • Author(s): Noritaka Chida
  • Organizer: The 11^<th> Florida Heterocyclic and Synthetic Conference
  • Place of Presentation: フロリダ大学(米国)
  • Year and Date: 2010-03-09
• [Presentation] Synthetic Study of (-)-Kainic Acid via Sequential Claisen-Overman Rearrangement (2009)
  • Author(s): Katsunori Kitamoto, Mana Sampei, Takaaki Sato, Noritaka Chida
  • Organizer: The 11th International Kyoto Conference on New Aspects of Organic Chemistry
  • Place of Presentation: リーガロイヤルホテル京都
  • Year and Date: 2009-11-11
• [Presentation] Synthetic Study of (-)-Kainic Acid via Sequential Claisen-Overman Rearrangement (2009)
  • Author(s): Katsunori Kitamoto, Mana Sampei, Takaaki Sato, Noritaka Chida
  • Organizer: The 11th International Kyoto Conference on New Aspects of Organic Chemistry
  • Place of Presentation: リーガロイヤルホテル京都.
  • Year and Date: 2009-11-11
• [Presentation] Overman転位ならびにそのカスケード型反応を利用した生物活性アルカロイド類の全合成 (2009)
  • Author(s): 濱直人, 松田知樹, 三輪祥平, 佐藤隆章, 千田憲孝
  • Organizer: 第51回天然有機化合物討論
  • Place of Presentation: 名古屋市公会堂
  • Year and Date: 2009-10-08
• [Presentation] Overman転位ならびにそのカスケード型反応を利用した生物活性アルカロイド類の全合成 (2009)
  • Author(s): 濱直人, 松田知樹, 三輪祥平, 佐藤隆章, 千田憲孝
  • Organizer: 第51回天然有機化合物討論会
  • Place of Presentation: 名古屋市公会堂
  • Year and Date: 2009-10-08
• [Presentation] Overman転位を鍵反応としたsalinosporamide AならびにA-315675の全合成研究 (2008)
  • Author(s): 千田 憲孝
  • Organizer: 第50回天然有機化合物討論会
  • Place of Presentation: 福岡国際会議場(福岡市)
  • Year and Date: 2008-10-01
• [Book] Chemistry of Opioids (2011)
  • Author(s): Noritaka Chida
  • Publisher: Springer
• [Remarks] 千田研究室ホームページ
• [Remarks]
  • URL: http://www/applc.keio.ac.jp/~chida/
• [Remarks]
  • URL: http://www/applc.keio.ac.jp/~chida/
• [Remarks]
  • URL: http://www.applc.keio.ac.jp/~chida/