Development of novel cyclization reactions via formation of ruthenacycle intermediate and their application to organic synthesis

• Project/Area Number: 26460002
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Chemical pharmacy
• Research Institution: Meiji Pharmaceutical University (2015-2016); Hokkaido University (2014)
• Principal Investigator: Saito Nozomi 明治薬科大学, 薬学部, 教授 (80349258)
• Project Period (FY): 2014-04-01 – 2017-03-31
• Project Status: Completed (Fiscal Year 2016)
• Budget Amount: ¥5,070,000 (Direct Cost: ¥3,900,000、Indirect Cost: ¥1,170,000); Fiscal Year 2016: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000); Fiscal Year 2015: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000); Fiscal Year 2014: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
• Keywords: 環化反応 / ルテニウム / メタラサイクル / アレン / アルキン / 環状化合物 / 天然物合成 / アルカロイド / ルテナサイクル / ルテニウムカルベン / 配位子

Outline of Final Research Achievements

Studies on the development of the novel cyclization reactions via ruthenacyclopentene intermediate formed by oxidative cyclization of allene and alkyne were conducted. Furthermore, we performed synthetic studies on indole alkaloids by using the above our ruthenium-catalyzed cyclization as a key step.

Research Products

• [Journal Article] Self-assembled Multi-layer Stabilized Nickel Nanoparticle Catalyst for Ligand-free Cross-coupling Reactions: in situ Metal Nanoparticle and Nanospace Simultaneous Organization (2016)
  • Author(s): Naoyuki Hoshiya, Katsumasa Fujiki, Takahisa Taniguchi, Tetsuo Honma, Yusuke Tamenori, Mincen Xiao, Nozomi Saito, Mami Yokoyama, Akira Ishii, Hiromichi Fujioka, Satoshi Shuto, Yoshihiro Sato, Mitsuhiro Arisawa
  • Journal Title: Adv. Synth. Catal. Volume: 358 Issue: 15 Pages: 2449-2459
  • DOI: 10.1002/adsc.201600024
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Enantioselective Synthesis of β-Amino Acid Derivatives via Nickel-Promoted Regioselective Carboxylation of Ynamides and Rhodium-Catalyzed Asymmetric Hydrogenation (2016)
  • Author(s): Nozomi Saito, Iman Abdullah, Kayoko Hayashi, Katsuyuki Hamada, Momoko Koyama, Yoshihiro Sato
  • Journal Title: Org. Biomol. Chem. Volume: 14 Issue: 42 Pages: 10080-10089
  • DOI: 10.1039/c6ob01234e
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Nickel-Promoted Highly Regioselective Carboxylation of Aryl Ynol Ether and Its Application to the Synthesis of Chiral β-Aryloxypropionic Acid Derivatives (2015)
  • Author(s): 齋藤 望、孫 仲冬、佐藤美洋
  • Journal Title: Chemistry an Asian Journal Volume: 10 Issue: 5 Pages: 1170-1176
  • DOI: 10.1002/asia.201403399
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Double Carbonylation of Aryl Iodides with Amines under an Atmospheric Pressure of Carbon Monoxide Using Sulfur- Modified Au-Supported Palladium (2015)
  • Author(s): Nozomi Saito Takahisa Taniguchi, Naoyuki Hoshiya, Satoshi Shuto, Mitsuhiro Arisawa, Yoshihiro Sato
  • Journal Title: Green Chem. Volume: 17 Issue: 4 Pages: 2358-2361
  • DOI: 10.1039/c4gc02469a
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Presentation] スルホニウム種を用いたインドールの芳香族求核置換反応 (2017)
  • Author(s): 田湯正法, 野村和也, 河内晃樹, 樋口和宏, 齋藤望, 川﨑知己
  • Organizer: 日本薬学会第137年会
  • Place of Presentation: 東北大学川内北キャンパス（仙台市）
  • Year and Date: 2017-03-24
• [Presentation] From Stoichiometry to Catalysis: Hydrocarboxylation of Ynamides with Nickel Complex Employing CO2 (2017)
  • Author(s): Iman Abdullah, Ryohei Doi, Nozomi Saito, Yoshihiro Sato
  • Organizer: 日本化学会第97春季年会
  • Place of Presentation: 慶應義塾大学日吉キャンパス（横浜市）
  • Year and Date: 2017-03-16
• [Presentation] アレンインの触媒的環化二量化反応による 光学活性C2 対称ラダー状分子の合成 (2016)
  • Author(s): 齋藤 望, 片桐光一, 花形 聡, 田湯正法, 佐藤美洋
  • Organizer: 第46回複素環化学討論会
  • Place of Presentation: 金沢歌劇座（金沢市）
  • Year and Date: 2016-09-26
• [Presentation] Nickel-Catalyzed Hydrocarboxylation of Alkynes and Styrenes Using Sulfur-Modified Au-Supported Nickel Nanoparticles Catalyst (SANi) (2016)
  • Author(s): Takahisa Taniguchi, Nozomi Saito, Naoyuki Hoshiya, Katsumasa Fujiki, Satoshi Shuto, Hiromichi Fujioka, Mitsuhiro Arisawa, and Yoshihiro Sato
  • Organizer: 27th International Conference on Organometallic Chemistry
  • Place of Presentation: Melbourne Convention and Exhibition Centre （メルボルン）
  • Year and Date: 2016-07-17
  • Int'l Joint Research
• [Presentation] 硫黄修飾金担持型ニッケル触媒SANiの開発と二酸化炭素固定化反応への利用 (2016)
  • Author(s): 谷口敬寿，齋藤 望，星谷尚亨，藤木勝将，周東 智，藤岡弘道，有澤光弘，佐藤美
  • Organizer: 第14回次世代を担う有機化学シンポジウム
  • Place of Presentation: 長井記念ホール（東京）
  • Year and Date: 2016-05-27
• [Presentation] Enantioselective Synthesis of β-Amino Acid Derivatives via Nickel-Mediated Carboxylation of Ynamides and Sequential Rhodium-Catalyzed Asymmetric Hydrogenation (2016)
  • Author(s): Nozomi Saito, Iman Abdullah, Kayoko Hayashi, Katsuyuki Hamada, Momoko Koyama,Yoshihiro Sato
  • Organizer: 26th French- Japanese Symposium on Medicinal and Fine Chemistry
  • Place of Presentation: 京王プラザホテル多摩（東京）
  • Year and Date: 2016-05-15
  • Int'l Joint Research
• [Presentation] Nucleophilic Aromatic Substitution on Electron-Rich Indoles Mediated by DMSO-Tf2O (2016)
  • Author(s): Masanori Tayu, Koki Kawachi, Kazuya Nomura, Kazuhiro Higuchi, Tomomi Kawasaki, Nozomi Saito
  • Organizer: 26th French- Japanese Symposium on Medicinal and Fine Chemistry
  • Place of Presentation: 京王プラザホテル多摩（東京）
  • Year and Date: 2016-05-15
  • Int'l Joint Research
• [Presentation] Sulfur-Modified Au-Supported Nickel Nanoparticles Catalyst (SANi)-Catalyzed Hydrocarboxylation of Alkynes (2015)
  • Author(s): 谷口敬寿、齋藤 望、星谷尚亨、藤木勝征、周東 智、藤岡弘道、有澤光弘、佐藤美洋
  • Organizer: IKCOC13
  • Place of Presentation: 京都市
  • Year and Date: 2015-11-09
  • Int'l Joint Research
• [Presentation] アブダラ イマン、齋藤 望、林香代子、濱田勝征、小山桃子、佐藤美洋 (2015)
  • Author(s): Nickel-Mediated and -Catalyzed Carboxylation of Ynamide and Its Application to the Enantioselective Synthesis of b-Amino Acis Derivatives
  • Organizer: IKCOC13
  • Place of Presentation: 京都市
  • Year and Date: 2015-11-09
  • Int'l Joint Research
• [Presentation] Nickel-Catalyzed Carboxylation of Alkynes Using Sulfur-Modified Au-Supported Nickel Nanoparticles Catalyst (SANi) (2015)
  • Author(s): 谷口敬寿、齋藤 望、星谷尚亨、藤木勝征、周東 智、本間徹生、藤岡弘道、有澤光弘、佐藤美洋
  • Organizer: OMCOS18
  • Place of Presentation: バルセロナ市（スペイン）
  • Year and Date: 2015-06-28
  • Int'l Joint Research
• [Presentation] 淡路直矢、田口直人、齋藤 望、谷口敬寿、佐藤美洋 (2015)
  • Author(s): Nickel-Promoted Carboxylation of Alkenes: Synthesis of Acrylic Acid Derivatives
  • Organizer: OMCOS18
  • Place of Presentation: バルセロナ市（スペイン）
  • Year and Date: 2015-06-28
  • Int'l Joint Research
• [Presentation] 硫黄修飾金担持型ニッケル触媒の開発とアルキンへの二酸化炭素固定化反応の利用 (2015)
  • Author(s): 谷口敬寿、齋藤 望、星谷尚亨、本間徹生、周東 智、藤岡弘道、有澤光弘、佐藤 美洋
  • Organizer: 日本薬学会第135年会
  • Place of Presentation: 神戸
  • Year and Date: 2015-03-28 – 2015-03-30
• [Presentation] ニッケル錯体によるスチレン誘導体への二酸化炭素固定化反応の開発 (2015)
  • Author(s): 田口直人、齋藤 望、佐藤美洋
  • Organizer: 日本薬学会第135年会
  • Place of Presentation: 神戸
  • Year and Date: 2015-03-28 – 2015-03-30
• [Presentation] ニッケル錯体によるイノールエーテルのカルボキシル化と不斉水素化を経由した、 β - アリールオキシカルボン酸類のエナンチオ選択的合成 (2014)
  • Author(s): 齋藤 望、孫 仲冬、佐藤美洋
  • Organizer: 第40回反応と合成の進歩シンポジウム
  • Place of Presentation: 仙台
  • Year and Date: 2014-11-10 – 2014-11-11
• [Presentation] Transition Metal-Catalyzed Transformations of Ynamide and TheirApplication to Natural Product Synthesis (2014)
  • Author(s): 齋藤 望
  • Organizer: VIETNAM MALAYSIA INTERNATIONAL CHEMICAL CONGRESS
  • Place of Presentation: ハノイ（ベトナム）
  • Year and Date: 2014-11-07 – 2014-11-10
  • Invited
• [Presentation] Molecular Transformations of Ynamide and Their Application: Total Synthesis of (-)-Herbindoles (2014)
  • Author(s): 齋藤 望
  • Organizer: 18thMALAYSIAN INTERNATIONAL CHEMICAL CONGRESS
  • Place of Presentation: クアラルンプール（マレーシア）
  • Year and Date: 2014-11-03 – 2014-11-05
  • Invited
• [Presentation] Nickel(0)-Promoted Carboxylation of Aryl Ynol Ether with CO2 (2014)
  • Author(s): 孫 仲冬、齋藤 望、佐藤美洋
  • Organizer: ICOMC 2014
  • Place of Presentation: 札幌
  • Year and Date: 2014-07-13 – 2014-07-18
• [Presentation] Sulfur-Modified Au-Supported Palladium (SAPd) -Catalyzed Double Carbonylation of Aryl Iodides under Atmospheric CO Pressur (2014)
  • Author(s): 谷口敬寿、齋藤 望、星谷尚亨、周東 智、有澤光弘、佐藤美洋
  • Organizer: ICOMC 2014
  • Place of Presentation: 札幌
  • Year and Date: 2014-07-13 – 2014-07-18