Catalytic Asymmetric Cyclopropenation using New Dirhodium(II) Complexes

• Project/Area Number: 23790001
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Multi-year Fund
• Research Field: Chemical pharmacy
• Research Institution: Hokkaido University
• Principal Investigator: ANADA Masahiro 北海道大学, 大学院・薬学研究院, 准教授 (90344473)
• Project Period (FY): 2011 – 2012
• Project Status: Completed (Fiscal Year 2012)
• Budget Amount: ¥4,420,000 (Direct Cost: ¥3,400,000、Indirect Cost: ¥1,020,000); Fiscal Year 2012: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000); Fiscal Year 2011: ¥2,730,000 (Direct Cost: ¥2,100,000、Indirect Cost: ¥630,000)
• Keywords: 合成化学 / 不斉触媒反応 / ロジウム(II)錯体 / α-アルキル-α-ジアゾエステル / シクロプロペン化反応 / カルベン / シクロプロパン化反応 / フェニルアセチレン / シクロプロパン / DFT計算

Research Abstract

A new dirhodium(II) carboxylate complex [Rh_2(S-TBPTTL)_4] is an exceptionally effective catalyst for enantioselective cyclopropenation reactions of 1-alkynes with 2,4-dimethyl-3-pentyl α-alkyl-α-diazoacetates in preference to alkene formation via a 1,2-hydride shift, in which exceptionally high levels of asymmetric induction (up to 99% ee) as well as good to high chemoselectivities have been achieved.

Research Products

• [Journal Article] Catalytic Asymmetric Intermolecular C-H Insertion Reactions of 1,4-Cyclohexadiene with 2,4-Dimethyl-3-pentyl α-Alkyl-α-diazoacetates using Chiral Dirhodium(II) Carboxylates (2012)
  • Author(s): Goto, T.; Onozuka, T.; Kosaka, Y.; Anada, M.; Takeda, K.; Hashimoto, S.
  • Journal Title: Heterocycles Volume: 86 Issue: 2 Pages: 1647-1659
  • DOI: 10.3987/com-12-s(n)120
  • URL: http://dx.doi.org/
  • Peer Reviewed
• [Journal Article] A Polymer-Supported Chiral Fluorinated Dirhodium(II) Complex for Asymmetric Amination of Silyl Enol Ethers (2012)
  • Author(s): Oohara, T.
  • Journal Title: Adv. Synth. Catal. Volume: 354 Issue: 11-12 Pages: 2331-2338
  • DOI: 10.1002/adsc.201200219
  • URL: http://dx.doi.org/
  • Peer Reviewed
• [Journal Article] Enantio- and Diastereoselective Hetero-Diels-Alder Reactions between 2-Aza-3-silyloxy-1, 3-butadienes and Aldehydes Catalyzed by Chiral Dirhodium(II) Carboxamidates (2012)
  • Author(s): Y. Watanabe, T. Washio, J. Krishnamurthi, M. Anada and S. Hashimoto
  • Journal Title: Chemical Communications Volume: 48 Issue: 55 Pages: 6969-6971
  • DOI: 10.1039/c2cc32876c
  • URL: http://dx.doi.org/
  • Peer Reviewed
• [Journal Article] Enantio- and Diastereoselective Cyclopropanation with tert-Butyl α-Diazopropionate Catalyzed by Dirhodium(II) Tetrakis[N-tetrabromophthaloyl-(S)-tert-leucinate] (2011)
  • Author(s): Goto, T.; Takeda, K.; Anada, M.; Ando, K.; Hashimoto, S.
  • Journal Title: Tetrahedron Lett. Volume: 52 Issue: 32 Pages: 4200-4203
  • DOI: 10.1016/j.tetlet.2011.06.008
  • URL: http://dx.doi.org/
  • Peer Reviewed
• [Journal Article] Highly Enantioselective Cyclopropenation Reaction of 1-Alkynes with α-Alkyl-α-diazoesters Catalyzed by Dirhodium(II) Carboxylates (2011)
  • Author(s): Goto,T.; Takeda,K.；Shimada,N.;Nambu,H.; Anada,M;Shiro.M; Ando,.K; Hashimoto,S.
  • Journal Title: Angew. Chem. Int. Ed. Volume: 50 Issue: 30 Pages: 6803-6808
  • DOI: 10.1002/anie.201101905
  • URL: http://dx.doi.org/
  • Peer Reviewed
• [Presentation] Synthetic Studies of 18E-Lyngbyaloside C (2012)
  • Author(s): F. Tanada, Y. Watanabe, M. Anada, S.Hashimoto
  • Organizer: The Twelfth International Kyoto Conference on New Aspects of Organic Chemistry(IKCOC-12)
  • Place of Presentation: リーガロイヤルホテル(京都)
  • Year and Date: 2012-11-14
• [Presentation] Catalytic Asymmetric Synthesis of Tetrahydropyran Natural Products Using a Hetero-Diels-Alder Strategy (2012)
  • Author(s): M. Anada
  • Organizer: BIT's 3rd World Annual Congress of Catalytic Asymmetric Synthesis 2012
  • Place of Presentation: Beijing International Convention Center (中国)
  • Year and Date: 2012-05-14
• [Presentation] Catalytic Asymmetric Synthesis of Tetrahydropyran Natural Products Using a Hetero-Diels-Alder Strategy (2012)
  • Author(s): Anada, M.
  • Organizer: BIT’s 3rd Annual World Congress of Catalytic Asymmetric Synthesis 2012
  • Place of Presentation: Beijing International Convention Center, China
• [Presentation] Synthetic Studies of 18E-Lyngbyaloside C (2012)
  • Author(s): Anada, M.
  • Organizer: The Twelfth International Kyoto Conference on New Aspects of Organic Chemistry (IKCOC-12)
  • Place of Presentation: リーガロイヤルホテル（京都）
• [Book] 触媒的C-H活性化を機軸とする天然物合成,CSJカレントレビュー05 「不活性結合・不活性分子の活性化革新的な分子変換反応の開拓」 (2011)
  • Author(s): 穴田仁洋, 南部寿則, 橋本俊一
  • Publisher: 日本化学会編
• [Book] CSJカレントレビュー05 「不活性結合・不活性分子の活性化 革新的な分子変換反応の開拓」日本化学会編 (2011)
  • Author(s): 穴田仁洋他
  • Publisher: 化学同人
• [Remarks]
  • URL: http://www.pharm.hokudai.ac.jp/yakuzou/staff/anada.html
• [Patent(Industrial Property Rights)] Polymer-supported metal complex catalyst (2012)
  • Inventor(s): S. Hashimoto, M. Anada
  • Industrial Property Rights Holder: Hokkaido University
  • Acquisition Date: 2012-01-10
  • Overseas