Synthesis of Polymer-Supported Chiral Dirhodium (II) Complexes and Asymmetric Reactions Using These Catalysts

• Project/Area Number: 20790002
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Single-year Grants
• Research Field: Chemical pharmacy
• Research Institution: Hokkaido University
• Principal Investigator: NAMBU Hisanori Hokkaido University, 大学院・薬学研究院, 助教 (80399956)
• Project Period (FY): 2008 – 2009
• Project Status: Completed (Fiscal Year 2009)
• Budget Amount: ¥4,420,000 (Direct Cost: ¥3,400,000、Indirect Cost: ¥1,020,000); Fiscal Year 2009: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000); Fiscal Year 2008: ¥2,730,000 (Direct Cost: ¥2,100,000、Indirect Cost: ¥630,000)
• Keywords: 有機化学 / 合成化学 / 不斉触媒反応 / 固相遷移金属 / ロジウム(II)錯体 / ラジカル重合反応 / アミノ化反応 / 1, 3-双極付加環化反応 / 1,3-双極付加環化反応 / カルボニルイリド / ナイトレン / ロジム(II)錯体 / C-H挿入反応 / カルベン

Research Abstract

Synthesis of polymer-supported Rh_2(S-TFPTTL)_4 and Rh_2(S-TCPTTL)_4, the fluorinated or chlorinated analogues of Rh_2(S-PTTL)_4, has been achieved. Asymmetric amination of silyl enol ether and asymmetric 1,3-dipolar cycloaddition of carbonyl ylide using these polymer-supported Rh (II) complexes afforded similar product yields and enantioselectivities as those found with homogeneous Rh_2(S-TFPTTL)_4 and Rh_2(S-TCPTTL)_4.

Research Products

• [Journal Article] Stereocontrolled Construction of 1, 2-cis-α-Glycosidic Linkages Using Glycosyl Diphenyl Phosphates and Synthesis of α-Galactosylceramide KRN7000 (2010)
  • Author(s): Nambu, H.; Nakamura, S.; Suzuki, N.; Hashimoto, S.
  • Journal Title: Trends Glycosci. Glycotechnol 22 Pages: 26-40
  • Peer Reviewed
• [Journal Article] Catalytic Asymmetric Construction of the exo-7-Aryl-6, 8-dioxabicyclo[3. 2. 1]octane Framework of Psoracorylifols B and C Using a Carbonyl Ylide Cycloaddition Strategy (2010)
  • Author(s): Kurosaki, Y.; Shimada, N.; Anada, M.; Nambu, H.; Hashimoto, S.
  • Journal Title: Bull. Korean Chem. Soc. 31 Pages: 694-696
  • Peer Reviewed
• [Journal Article] Catalytic Asymmetric Construction of the exo-7-Aryl-6,8-dioxabicyclo-[3.2.1]octane Framework of Psoracorylifols B and C Using a Carbonyl Ylide Cycloaddition Strategy (2010)
  • Author(s): Y.Kurosaki, et al.
  • Journal Title: Bull.Korean Chem.Soc. 31 Pages: 694-696
  • Peer Reviewed
• [Journal Article] Asymmetric Synthesis of Neolignans (-)-epi-Conocarpan and (+)-Conocarpan via Rh(II)-Catalyzed C-H Insertion Process and Revision of the Absolute Configuration of (-)-epi-Conocarpan (2009)
  • Author(s): Natori, Y.; Tsutsui, H.; Sato, N.; Nakamura, S.; Nambu, H.; Shiro, M.; Hashimoto, S.
  • Journal Title: J. Org. Chem. 74 Pages: 4418-4421
  • Peer Reviewed
• [Journal Article] Asymmetric Approach to the Pentacyclic Skeleton of Aspidosperma Alkaloids via Enantioselective Intramolecular 1, 3-Dipolar Cycloaddition of Carbonyl Ylides Catalyzed by Chiral Dirhodium(II) Carboxylates (2009)
  • Author(s): Nambu, H.; Hikime, M.; Krishnamurthi, J.; Kamiya, M.; Shimada, N.; Hashimoto, S.
  • Journal Title: Tetrahedron Lett. 50 Pages: 3675-3678
  • Peer Reviewed
• [Journal Article] Asymmetric Formal Synthesis of (-)-Pancracine via Catalytic Enantioselective C-H Amination Process (2009)
  • Author(s): Anada, M.; Tanaka, M.; Shimada, N.; Nambu, H.; Yamawaki, M.; Hashimoto, S.
  • Journal Title: Tetrahedron 65 Pages: 3069-3077
  • Peer Reviewed
• [Journal Article] Asymmetric Approach to the Pentacyclic Skeleton of Aspidosperma Alkaloids via Enantioselective Intramolecular 1,3-Dipolar Cycloaddition of Carbonyl Ylides Catalyzed by Chiral Dirhodium(II)Carboxylate (2009)
  • Author(s): H.Nambu, et al.
  • Journal Title: Tetrahedron Lett. 50 Pages: 3675-3678
  • Peer Reviewed
• [Journal Article] Asymmetric Synthesis of Neolignans(-)-epi-Conocarpan and(+)-Conocarpan via Rh(II)-Catalyzed C-H Insertion Process and Revision of the Absolute Configuration of(-)-epi-Conocarpan (2009)
  • Author(s): Y.Natori, et al.
  • Journal Title: J.Org.Chem. 74 Pages: 4418-4421
  • Peer Reviewed
• [Journal Article] Asymmetric Formal Synthesis of (-)-Pancracine via Catalytic Enantioselective C-H Amination Process (2009)
  • Author(s): M.Anada, et al.
  • Journal Title: Tetrahedron 65 Pages: 3069-3077
  • Peer Reviewed
• [Journal Article] Catalytic Enantioselective Intermolecular Cycloaddition of 2-Diazo-3, 6-diketoester-Derived Carbonyl Ylides with Alkynes and Styrenes Using Chiral Dirhodium(II) Carboxylates (2008)
  • Author(s): Shimada, N.; Anada, M.; Nakamura, S.; Nambu, H.; Tsutsui, H.; Hashimoto, S.
  • Journal Title: Org. Lett. 10 Pages: 3603-3606
  • Peer Reviewed
• [Journal Article] Catalytic Stereoselective Glycosidation with Glycosyl Diphenyl Phosphates: Rapid Construction of 1, 2-cis-α-Glycosidic Linkages (2008)
  • Author(s): Koshiba, M.; Suzuki, N.; Arihara, R.; Tsuda, T.; Nambu, H.; Nakamura, S.; Hashimoto, S.
  • Journal Title: Chem. Asian J. 3 Pages: 1664-1677
  • Peer Reviewed
• [Journal Article] Catalytic Stereoselective Glycosidation with Glycosyl Diphenyl Phosphates : Rapid Construction of 1,2-cis-α-Glycosidic Linkages (2008)
  • Author(s): M.Koshiba, et al.
  • Journal Title: Chem.Asian J. 3 Pages: 1664-1677
  • Peer Reviewed
• [Journal Article] Catalytic Enantioselective Intermolecular Cycloaddition of 2-Diazo-3,6-diketoester-Derived Carbonyl Ylides with Alkynes and Styrenes Using Chiral Dirhodium(II) Carboxylates (2008)
  • Author(s): N.Shimada, et al.
  • Journal Title: Org.Lett. 10 Pages: 3603-3606
  • Peer Reviewed
• [Presentation] インドールを求双極子剤として用いるカルボニルイリドの分子間1, 3-双極付加環化反応 (2010)
  • Author(s): 嶋田修之, 南部寿則, 橋本俊一
  • Organizer: 日本薬学会第130年会
  • Place of Presentation: 岡山
  • Year and Date: 2010-03-28
• [Presentation] Asymmetric Approach to the Pentacyclic Skeleton of Aspidosperma Alkaloids via 1, 3-Dipolar Cycloaddition of Carbonyl Ylides Catalyzed by Chiral Rh(II) Complexes (2009)
  • Author(s): Nambu, H.; Hikime, M.; Kamiya, M.; Shimada, N.; Hashimoto, S.
  • Organizer: The 4th International Conference on Cutting-Edge Organic Chemistry in Asia (ICCEOCA-4)
  • Place of Presentation: Bangkok, Thailand
  • Year and Date: 2009-12-02
• [Presentation] Asymmetric Approach to the Pentacyclic Skeleton of Aspidosperma Alkaloids via 1,3-Dipolar Cycloaddition of Carbonyl Ylides Catalyzed by Chiral Rh(II)Complexes (2009)
  • Author(s): H.Nambu, et al.
  • Organizer: The 4th International Conference on Cutting-Edge Organic Chemistry in Asia(ICCEOCA-4)
  • Place of Presentation: Bangkok, Thailand
  • Year and Date: 2009-12-02
• [Presentation] グリコシルジフェニルホスファートを用いるグリコシル化反応の反応機構に関する研究 (2009)
  • Author(s): 本泉周一郎, 中村精一, 南部寿則, 橋本俊一
  • Organizer: 日本薬学会第129年会
  • Place of Presentation: 京都
  • Year and Date: 2009-03-27
• [Presentation] Catalytic Enantioselective Intramolecular 1, 3-Dipolar Cycloaddition of Carbonyl Ylide: Asymmetric Synthesis of Aspidosperma Skeleton (2008)
  • Author(s): Hikime, M.; Shimada, N.; Nambu, H.; Hashimoto, S.
  • Organizer: The 12th Japan-Korea Joint Symposium on Drug Design and Development
  • Place of Presentation: Sendai, Japan
  • Year and Date: 2008-05-15
• [Presentation] Catalytic Enantioselective Intramolecular 1,3-Dipolar Cycloaddition of Carbonyl Ylide : Asymmetric Synthesis of Aspidosperma Skeleton (2008)
  • Author(s): H.Nambu, et al.
  • Organizer: The 12th Japan-Korea Joint Symposium on Drug Design and Development
  • Place of Presentation: 仙台市戦災復興記念館 (仙台)
  • Year and Date: 2008-05-15
• [Book] Phosphates, Phosphites, and Other O-P Derivatives (Demchenko, A.V. Ed. ) (2008)
  • Author(s): Nakamura, S.; Nambu, H.; Hashimoto, S.
  • Publisher: Wiley-VCH
• [Book] Handbook of Chemical Glycosylation (2008)
  • Author(s): S.Nakamura, et al.
  • Publisher: Wiley-VCH