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2012 Fiscal Year Final Research Report

Efficient construction of organic molecular skeleton by using spiro-type catalysts

Research Project

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Project/Area Number 22350041
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Synthetic chemistry
Research InstitutionOsaka University

Principal Investigator

SASAI Hiroaki  大阪大学, 産業科学研究所, 教授 (90205831)

Co-Investigator(Kenkyū-buntansha) TAKENAKA Kazuhiro  大阪大学, 産業科学研究所, 助教 (20423113)
TAKIZAWA Shinobu  大阪大学, 産業科学研究所, 准教授 (50324851)
Project Period (FY) 2010 – 2012
Keywords有機化学 / 合成化学 / 触媒 / キラル配位子 / 分子認識
Research Abstract

We have developed a unique chiral ligand SPRIX (1), possessing isoxazoline coordination sites on a rigid spiro backbone. The good affinity of SPRIX towards Pd(II) and its high stability under acidic and oxidative conditions encouraged us to explore new asymmetric Pd catalysis.Herein, we have developed an enantioselective oxidative sequential reaction of alkynyl cyclohexadienones 2 catalyzed by Pd-SPRIX complex, which involves an unusual carboxylation of Pd enolate intermediate. The reaction of 2 in the presence of 10 mol % of Pd(OAc)2 and 15 mol % of (M,S,S)-i-Pr-SPRIX (1d) under an oxygen atmosphere (1 atm) in a 9:1 mixture of AcOH-toluene at 60 °C proceeded smoothly to give product 3 in good yields with up to 71% ee. We have also developed a novel enantioselective Pd(II)/Pd(IV) catalysis of alkenyl alcohols utilizing 1,1-diphenylbut-3-en-1-ol (4), leading to optically active 4-acetoxy-5,5-diphenyltetrahydrofuran (5) in 92% yield with 90% ee.

  • Research Products

    (37 results)

All 2013 2012 2011 2010 Other

All Journal Article (20 results) (of which Peer Reviewed: 20 results) Presentation (13 results) Book (3 results) Remarks (1 results)

  • [Journal Article] Facile Synthesis of α-Methylidene-γ-Butyrolactones: Intramolecular Rauhut-Currier Reaction Promoted by Chiral Acid-Base Organocatalysts2013

    • Author(s)
      Takizawa, S.; Nguyen, T. M.-N.; Grossmann, A.; Suzuki, M.; Enders, D.; Sasai H
    • Journal Title

      Tetrahedron

      Volume: 69 Pages: 1202-1209

    • Peer Reviewed
  • [Journal Article] Vanadium-Catalyzed Enantioselective Friedel-Crafts-Type Reactions2013

    • Author(s)
      Takizawa, S.; Arteaga, F. A.; Yoshida, Y.; Kodera, J.; Nagata, Y.; Sasai, H.
    • Journal Title

      Dalton Trans

      Volume: (in press)

    • DOI

      DOI:10.1039/C2DT32202A

    • Peer Reviewed
  • [Journal Article] DFT Study on 5-Endo-Trig-Type Cyclization of 3-Alkenoic Acids Using Pd-SPRIX Catalyst: Importance of the Rigid Spiro Framework for Both Selectivity and Reactivity2013

    • Author(s)
      Gabr, R. K. M.; Hatakeyama, T.; Takenaka, K.; Takizawa, S.; Okada, Y.; Nakamura, M.; Sasai, H.
    • Journal Title

      Chem. Eur. J

      Volume: (in press)

    • DOI

      DOI:10.1002/chem.201203189

    • Peer Reviewed
  • [Journal Article] o-(Hydroxyalkyl) P-Chirogenic Phosphines as Functional Chiral Lewis Bases2013

    • Author(s)
      Remond, E.; Bayardon, J.; Takizawa, S.; Rousselin, Y.; Sasai, H.; Juge, S
    • Journal Title

      Org. Lett

      Volume: 15 Pages: 1870-1873

    • Peer Reviewed
  • [Journal Article] Enantioselective Multicatalytic Synthesis of α-Benzyl-β-hydroxyindan-1-ones2013

    • Author(s)
      Suzuki, T.; Ishizaka, Y.; Ghozati, K.; Zhou, D.-Y.; Asano, K.; Sasai, H
    • Journal Title

      Synthesis

      Volume: (in press)

    • DOI

      DOI:10.1055/s-0033-1338479

    • Peer Reviewed
  • [Journal Article] Enantioselective Synthesis of α-Alkylidene-γ-Butyrolactones: Intramolecular Rauhut-Currier Reaction Promoted by Acid/Base Organocatalysts2012

    • Author(s)
      Takizawa, S.; Nguyen, T. M.-N.Grossmann, A.; Enders, D.; Sasai H
    • Journal Title

      Angew. Chem., Int. Ed

      Volume: 51 Pages: 5423-5426

    • Peer Reviewed
  • [Journal Article] Design and Synthesis of Spiro Bis(1,2,3-triazolium) Salts As Chiral Ionic Liquids2012

    • Author(s)
      Yoshida, Y.; Takizawa, S.; Sasai, H.
    • Journal Title

      Tetrahedron: Asymmetry

      Volume: 23 Pages: 843-851

    • Peer Reviewed
  • [Journal Article] Pd(II)-SPRIX Catalyzed Enantioselective Construction of Pyrrolizines/Pyrroloindoles Employing Molecular Oxygen As the Sole Oxidant, Ramalingan, C2011

    • Author(s)
      Takenaka, K.; Sasai, H
    • Journal Title

      Tetrahedron

      Volume: 67 Pages: 2889-2894

    • Peer Reviewed
  • [Journal Article] Chlorinative Cyclization of 1,6-Enynes by Enantioselective Palladium(II)/Palladium(IV) Catalysis2011

    • Author(s)
      Takenaka, K.; Hashimoto, S.; Takizawa, S.; Sasai, H
    • Journal Title

      Adv. Synth. Catal.

      Volume: 353 Pages: 1067-1070

    • Peer Reviewed
  • [Journal Article] Enantioselective Cyclization of 4-Alkenoic Acids via an Oxidative Allylic C-H Esterification2011

    • Author(s)
      Takenaka, K.; Akita, M.; Tanigaki, Y.; Takizawa, S.; Sasai, H.
    • Journal Title

      Org. Lett

      Volume: 13 Pages: 3506-3509

    • Peer Reviewed
  • [Journal Article] A Bifunctional Spiro-Type Organocatalyst with High Enantiocontrol: Application to the Aza-Morita-Baylis-Hillman Reactions2011

    • Author(s)
      Takizawa, S.; Kiriyama, K.; Ieki, K.; Sasai, H.
    • Journal Title

      Chem. Commun

      Volume: 47 Pages: 9227-9229

    • Peer Reviewed
  • [Journal Article] Synthesis of Spiro Bis(1,2,3-triazolium) Salts As Chiral Ionic Liquids2011

    • Author(s)
      Yoshida, Y.; Takizawa, S.; Sasai, H
    • Journal Title

      Tetrahedron Lett

      Volume: 52 Pages: 6877-6879

    • Peer Reviewed
  • [Journal Article] An Enantioselective Organocatalyzed aza-MBH Domino Process: Application to the Facile Synthesis of Tetrahydropyridines2011

    • Author(s)
      Takizawa, S.; Inoue, N.; Sasai H
    • Journal Title

      Tetrahedron Lett

      Volume: 52 Pages: 377-380

    • Peer Reviewed
  • [Journal Article] Asymmetric Synthesis of Chiral Spiro Bis(isoxazoline) and Spiro (Isoxazole-Isoxazoline) Ligands2010

    • Author(s)
      Takenaka, K.; Nagano, T.; Takizawa, S.; Sasai, H.Tetrahedron
    • Journal Title

      Asymmetry

      Volume: 21 Pages: 379-381

    • Peer Reviewed
  • [Journal Article] Enantioselective 6-Endo-Trig Wacker-Type Cyclization of 2-Geranylphenols: Application to Facile Synthesis of (-)-Cordiachromene2010

    • Author(s)
      Takenaka, K.; Tanigaki, Y.; Patil, M. L.; Rao, C. V. L.; Takizawa, S.; Suzuki, T.; Sasai, H
    • Journal Title

      Tetrahedron: Asymmetry

      Volume: 21 Pages: 767-770

    • Peer Reviewed
  • [Journal Article] Acid-Base Organocatalysts for the Aza-Morita-Baylis-Hillman Reaction of Nitroalkenes2010

    • Author(s)
      Takizawa, S.; Horii, A.; Sasai, H.
    • Journal Title

      Tetrahedron: Asymmetry

      Volume: 21 Pages: 891-894

    • Peer Reviewed
  • [Journal Article] Enantioselective Wacker-Type Cyclization of 2-Alkenyl-1,3-Diketones Promoted by Pd-SPRIX Catalyst S. C.; Patil, M. L.; Rao, C. V. L2010

    • Author(s)
      Takizawa, S.; Suzuki, T.; Sasai, H.
    • Journal Title

      Org. Lett

      Volume: 12 Pages: 3480-3483

    • Peer Reviewed
  • [Journal Article] Formal Total Synthesis of Ottelione Using Iridium-Catalyzed Oxidative Desymmetrization2010

    • Author(s)
      Suzuki, T.; Ghozati, K.; Zhou, D.-Y.; Katoh, T.; Sasai, H
    • Journal Title

      Tetrahedron

      Volume: 66 Pages: 7562-7568

    • Peer Reviewed
  • [Journal Article] Enantioselective Synthesis of Isoindolines: Organocatalyzed Domino Process Based on the aza-Morita-Baylis-Hillman (aza-MBH) Reaction2010

    • Author(s)
      Takizawa, S.; Inoue, N.; Hirata, S.; Sasai H
    • Journal Title

      Angew. Chem. Int. Ed

      Volume: 49 Pages: 9725-9729

    • Peer Reviewed
  • [Journal Article] Pd-Catalyzed 5-Endo-Trig-Type Cyclization of b,g-Unsaturated Carbonyl Compounds: an Efficient Ring Closing Reaction to Give g-Butenolides and 3-Pyrrolin-2-ones2010

    • Author(s)
      Bajracharya, G. B.; Koranne, P. S.; Nadaf, R. N.; Gabr, R. K. M.; Takenaka, K.; Takizawa, S.; Sasai H
    • Journal Title

      Chem. Commun

      Volume: 46 Pages: 9064-9066

    • Peer Reviewed
  • [Presentation] Enantioselective Organocatalyzed Aza-Morita-Baylis-Hillman (Aza-MBH) Reaction of Ketimines2012

    • Author(s)
      Takizawa, S.; Arteaga-Arteaga, F.; Yoshida, Y.; Vellaisamy, S.; Remond, E.; Bayardon, J.; Juge, S.; Sasai, H
    • Organizer
      First Japan-USA Organocatalytic Symposium
    • Place of Presentation
      Hawaii, USA
    • Year and Date
      20121215-18
  • [Presentation] Development of Chiral Spiro Bis(isoxazoline) Ligand "SPRIX"2012

    • Author(s)
      Sasai, H.
    • Organizer
      Cambodian Malaysian Chemical Conference (CMCC) 2012
    • Place of Presentation
      Siem Reap, Cambodia
    • Year and Date
      20121019-21
  • [Presentation] Dual Activation In Asymmetric Organocatalyses2012

    • Author(s)
      Sasai, H
    • Organizer
      17th Malaysian Chemical Congress (17MCC)
    • Place of Presentation
      Kuala Lumpur, Malaysia
    • Year and Date
      20121015-17
  • [Presentation] Umpolung Reactivity of Pd Enolate: Cyclative Diacetoxylation of Alkynyl Cyclohexadienones Catalyzed by Pd-SPRIX2012

    • Author(s)
      Takenaka, K.; Mohanta, S. C.; Takizawa, S.; Sasai, H
    • Organizer
      The 6th Kansai-CMDS Meeting on OMCOS
    • Place of Presentation
      Gangwon-do, Korea
    • Year and Date
      20120921-23
  • [Presentation] Enantioselective C-C Bond-forming Reactions Catalyzed by Vanadium(V) Complexes2012

    • Author(s)
      Sasai, H; Takizawa, S.; Kodera, J
    • Organizer
      8th International Vanadium Symposium ChemistryBiological Chemistry, & Toxicology (V8)
    • Place of Presentation
      Washington DC, USA
    • Year and Date
      20120815-18
  • [Presentation] Development of Enantioselective Carbon-Carbon Bond Forming Reactions Using Multi-functional Organocatalyst2012

    • Author(s)
      Sasai, H.
    • Organizer
      International Conference on Functional Organic Materials and Related Devices
    • Place of Presentation
      Hsinchu, Taiwan
    • Year and Date
      20120616-17
  • [Presentation] Development of Chiral Spiro Bis(isoxazoline) Ligand "SPRIX2012

    • Author(s)
      Sasai, H
    • Organizer
      BIT's 3rd Annual World Congress of Catalytic Asymmetric Synthesis-2012
    • Place of Presentation
      Beijin, China
    • Year and Date
      20120512-14
  • [Presentation] Exploring Novel Enantioselective Domino Reactions Promoted by Bifunctional Organocatalysts2012

    • Author(s)
      Sasai, H
    • Organizer
      3rd International Symposium on Organic Synthesis and Drug Development (ISOSDD2012)
    • Place of Presentation
      Changzhou, China
    • Year and Date
      20120320-23
  • [Presentation] Catalytic Enantioselective Reactions via Pd(II/IV) Catalysis2011

    • Author(s)
      H. Sasai
    • Organizer
      14th Asian Chemical Congress 2011
    • Place of Presentation
      Bangkok, Thailand
    • Year and Date
      20110905-08
  • [Presentation] Development of Enantioselective Catalyses Using Chiral Spiro Compounds2011

    • Author(s)
      H. Sasai
    • Organizer
      Chirality 2011
    • Place of Presentation
      Liverpool, UK
    • Year and Date
      20110710-13
  • [Presentation] 多機能不斉触媒の開発と触媒的不斉反応への応用2011

    • Author(s)
      笹井宏明
    • Organizer
      Symposium on Molecular Chirality 2011
    • Place of Presentation
      東京工業大学(東京)
    • Year and Date
      20110520-21
  • [Presentation] 新規エナンチオ選択的触媒反応系の開拓2011

    • Author(s)
      笹井宏明
    • Organizer
      海道大学GCOE-第17回精密合成化学セミナー ジョイントシンポジウム
    • Place of Presentation
      北海道大学(北海道)
    • Year and Date
      2011-12-19
  • [Presentation] Exploring a New Asymmetric Reaction Using Chiral Spiro Bis(isoxazoline) Ligand"SPRIX"2011

    • Author(s)
      H. Sasai
    • Organizer
      The International Symposium on Physical Organic Chemistry and Synthetic Materials
    • Place of Presentation
      Tianjin, China
    • Year and Date
      2011-07-02
  • [Book] Direct C-C Bond Formation (Henry, aza-Henry)2012

    • Author(s)
      Sasai, H
    • Total Pages
      214-242
    • Publisher
      In Comprehensive Chirality; Yamamoto, H.; Carreira, E., Eds. ELSEVIER Ltd, UK, 2012; Volume 4 (Synthetic Methods III - Catalytic Methods: C-C Bond Formation)
  • [Book] Morita-Baylis-Hillman Reaction2012

    • Author(s)
      Sasai, H.; Takizawa, S.
    • Total Pages
      234-263
    • Publisher
      In ComprehensiveChirality; Yamamoto, H.; Carreira, E., Eds. ELSEVIER Ltd, UK, 2012; Volume 6 (Synthetic Methods V - Organocatalysis)
  • [Book] Immobilization of Multicomponent Asymmetric Catalysts (MACs)2011

    • Author(s)
      Takizawa, S.; Sasai, H. John Wiley & Sons
    • Total Pages
      293-322
    • Publisher
      Polymeric Chiral Catalyst Design and Chiral Polymer Synthesis」(Itsuno, S. Ed.)
  • [Remarks]

    • URL

      http://www.sanken.osaka-u.ac.jp/labs/soc/socmain.html

URL: 

Published: 2014-08-29  

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