Highly Stereocontrolled Construction of Acyclic Systems Utilizing Titanocene Complexes as Synthetic Devices

• Project/Area Number: 21350026
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Organic chemistry
• Research Institution: Tokyo University of Agriculture and Technology
• Principal Investigator: TAKEDA Takeshi 東京農工大学, 大学院・工学研究院, 教授 (40111455)
• Project Period (FY): 2009 – 2011
• Project Status: Completed (Fiscal Year 2011)
• Budget Amount: ¥19,370,000 (Direct Cost: ¥14,900,000、Indirect Cost: ¥4,470,000); Fiscal Year 2011: ¥3,900,000 (Direct Cost: ¥3,000,000、Indirect Cost: ¥900,000); Fiscal Year 2010: ¥3,770,000 (Direct Cost: ¥2,900,000、Indirect Cost: ¥870,000); Fiscal Year 2009: ¥11,700,000 (Direct Cost: ¥9,000,000、Indirect Cost: ¥2,700,000)
• Keywords: 合成有機化学 / アリルチタノセン / 連続不斉中心 / 第四級炭素 / 立体選択性 / 立体特異性 / チタンカルベン錯体 / ジエニルシラン / 共役トリエン / チタナシクロブタン / チタナシクロペンテン / チタナシクロブテン / ホモアリルアルコール / ジエン / アレニルチタノセン / 不飽和エステル

Research Abstract

New processes for the stereocontrolled construction of acyclic systems bearing consecutive stereogenic centers and highly conjugated systems utilizing various titanocene complexes such as allyltitanocenes, alkylidenetitanocenes, and titanacycles as synthetic devices.

Research Products

• [Journal Article] Highly Diastereoselective Addition of Allyltitanocenes toα-Chiral Ketones (2012)
  • Author(s): T. Takeda, S. Yoshida, T. Nishimura, A. Tsubouchi
  • Journal Title: Tetrahedron Lett Volume: (in press)
  • Peer Reviewed
• [Journal Article] Highly Diastereoselective Construction of Acyclic Systems with Two Consecutive Quaternary Stereocenters by Allylation of Ketones (2012)
  • Author(s): T. Takeda, M. Yamamoto, S. Yoshida, A. Tsubouchi
  • Journal Title: Angew. Chem. Int. Ed Volume: (in press)
  • Peer Reviewed
• [Journal Article] Diastereoselective Addition of Allyltitanocenes to Cyclic Enones (2012)
  • Author(s): T. Takeda, T. Nishimura, S. Yoshida, F. Saiki, Y. Tajima, A. Tsubouchi
  • Journal Title: Org. Lett Volume: 14 Issue: 8 Pages: 2042-2045
  • DOI: 10.1021/ol300562g
  • Peer Reviewed
• [Journal Article] Diastereoselective Addition of Allyltitanocenes to Cyclic Enones (2012)
  • Author(s): T.Takeda, T.Nishimura, S.Yoshida, F.Saiki, Y.Tajima, A.Tsubouchi
  • Journal Title: Org.Lett. Volume: 14(in press)
  • Peer Reviewed
• [Journal Article] Regio-and Stereoselective Synthesis of 1, 4-Dienes (2011)
  • Author(s): S. Oishi, K. Hatano, A. Tsubouchi, T. Takeda
  • Journal Title: Chem. Commun Volume: 47 Issue: 42 Pages: 11639-11640
  • DOI: 10.1039/c1cc14765j
  • Peer Reviewed
• [Journal Article] Regio-and Stereoselective Preparation of Highly Substi-tuted Tertiary Homoallylic Alcohols (2011)
  • Author(s): T. Takeda, H. Wasa, A. Tsubouchi
  • Journal Title: Tetrahedron Lett Volume: 52 Pages: 4575-4578
  • Peer Reviewed
• [Journal Article] Highly Stereoselective Construction of Multiple Stereogenic Centers Using Allylic Sulfides (2011)
  • Author(s): T. Takeda, Y. Yatsumonji, T. Nishimura, T. Sugita, A. Tsubouchi
  • Journal Title: Phosphorus, Sulfur and Silicon and the Related Elements Volume: 186 Issue: 5 Pages: 1229-1233
  • DOI: 10.1080/10426507.2010.507727
• [Journal Article] Stereo-selective Formation of Phenylthio Groups Substituted 1-Metalla-3-titanacyclobutanes (2011)
  • Author(s): S. Oishi, A. Tsubouchi, T. Takeda
  • Journal Title: J. Organomet. Chem Volume: 696 Issue: 2 Pages: 581-585
  • DOI: 10.1016/j.jorganchem.2010.09.080
  • Peer Reviewed
• [Journal Article] Regio- and Stereoselective Preparation of Highly Substituted Tertiary Homoallylic Alcohols (2011)
  • Author(s): T.Takeda, H.Wasa, A.Tsubouchi
  • Journal Title: Tetrahedron Lett. Volume: 52 Issue: 35 Pages: 4575-4578
  • DOI: 10.1016/j.tetlet.2011.06.111
  • Peer Reviewed
• [Journal Article] Stereoselective formation of phenylthio groups substituted 1-metalla-3-titanacyclobutanes (2011)
  • Author(s): Shigeki Oishi
  • Journal Title: J.Organomet.Chem. Volume: 696 Pages: 581-585
  • Peer Reviewed
• [Journal Article] [2+2+1] Cycloaddition between Alkynes, Acry-lates, and Titanocene(II): Regioselective For-mation of 5-Alkoxycarbonyltitanacyclopent-2-enes and Their Addition to Carbonyls (2010)
  • Author(s): S. Oishi, K. Ohomika, A. Tsubouchi, T. Takeda
  • Journal Title: Chem. Lett Volume: 39 Issue: 7 Pages: 723-725
  • DOI: 10.1246/cl.2010.723
  • NAID: 10027182620
  • Peer Reviewed
• [Journal Article] Preparation of syn-Tertiary Homoallylic Alcohols Utilizing Allenyltitanocenes Generated by Reductive Titanation ofγ-Trimethylsilyl-propargylic Carbonates (2010)
  • Author(s): Y. Yatsumonji, T. Sugita, A. Tsubouchi, T. Takeda
  • Journal Title: Org. Lett Volume: 12 Issue: 9 Pages: 1968-1971
  • DOI: 10.1021/ol100395n
  • Peer Reviewed
• [Journal Article] Highly Stereoselective Preparation of Tertiary Homoallylic Alcohols Having Multi-Stereogenic Centers (2010)
  • Author(s): T. Takeda, T. Nishimura, Y. Yatsumonji, K. Noguchi, A. Tsubouchi
  • Journal Title: Chem. Eur. J Volume: 16 Issue: 16 Pages: 4729-4732
  • DOI: 10.1002/chem.201000101
  • Peer Reviewed
• [Journal Article] [2+2+1] Cycloaddition between Alkynes, Acrylates, and Titanocene(II) : Regioselective Formation of 5-Alkoxycarbonyltitanacyclonent-2-enes and Their Addition to Carbonyls (2010)
  • Author(s): Shigeki Oishi
  • Journal Title: Chem.Lett. Volume: 39 Pages: 723-725
  • Peer Reviewed
• [Journal Article] Highly Stereoselective Preparation of Tertiary Homoallylic Alcohols Having Multi-Stereogenic Centers (2010)
  • Author(s): Takeshi Takeda
  • Journal Title: Chem.Eur.J 16 Pages: 4729-4732
  • Peer Reviewed
• [Journal Article] Preparation of syn-Tertiary Homoallylic Alcohols Utilizing Allenyltitanocenes Generated by Reductive Titanation of γ-Trimethylsilylpropargylic Carbonates (2010)
  • Author(s): Yasutaka Yatsumonji
  • Journal Title: Org.Lett. 12 Pages: 1968-1971
  • Peer Reviewed
• [Journal Article] Regio-and Stereoselective Formation of Conjugated Dienes by Titanocene(II)-Promoted Alkylation of Propargyl Carbonates (2009)
  • Author(s): Y. Yatsumonji, Y. Atake, A. Tsubouchi, T. Takeda
  • Journal Title: Chem. Commun Issue: 23 Pages: 3375-3377
  • DOI: 10.1039/b905782j
  • Peer Reviewed
• [Journal Article] Highly Diastereoselective Addition of Allyltitanocenes to Ketones (2009)
  • Author(s): Y. Yatsumonji, T. Nishimura, A. Tsubouchi, K. Noguchi, T. Takeda
  • Journal Title: Chem. Eur. J Volume: 15 Issue: 11 Pages: 2680-2686
  • DOI: 10.1002/chem.200802340
  • Peer Reviewed
• [Presentation] アリルチタノセンとケトンの反応による連続する二つの第四級炭素の立体選択的構築 (2012)
  • Author(s): 武田猛,山本雅納,吉田理史,坪内彰
  • Organizer: 日本化学会弟92春季年会
  • Place of Presentation: 慶応大学矢上キャンパス(神奈川県)
  • Year and Date: 2012-03-28
• [Presentation] 二価チタノセンにより促進されるβ-シリルチオアセタールとアルキンの反応によるジエニルシランの合成 (2012)
  • Author(s): 坪内彰, 森絢子, 森重奈々, 武田猛
  • Organizer: 日本化学会弟92春季年会
  • Place of Presentation: 慶応大学矢上キャンパス(神奈川県)
  • Year and Date: 2012-03-26
• [Presentation] チタナシクロペンテンを経由する(Z)-アルケニルスルホンとヘテロ原子置換アレンの反応 (2011)
  • Author(s): 畠野圭介, 大石茂樹, 坪内彰, 武田猛
  • Organizer: 第58回有機金属化学討論会
  • Place of Presentation: 名古屋大学東山キャンパス(愛知県)
  • Year and Date: 2011-09-08
• [Presentation] Highly stereoselective construction of multiple stereogenic centers by the reactions of allyl-and allenyltitanocenes with ketones (2010)
  • Author(s): Takeshi Takeda
  • Organizer: 2010 International Chemical Congress of Pacific Basin Societies
  • Place of Presentation: Honolulu, USA
  • Year and Date: 2010-12-15
• [Presentation] Highly stereoselective construction of multiple stereogenic centers by the reactions of allyl-and allenyltitanocenes with ketones (2010)
  • Author(s): Takeshi Takeda
  • Organizer: 2010 International Chemical Congress of Pacific Basin Societies
  • Place of Presentation: Honolulu, USA 招待講演
  • Year and Date: 2010-12-15
• [Presentation] Organosulfur Compounds in Acyclic Stereoselection (2010)
  • Author(s): Takeshi Takeda
  • Organizer: XII National Symposium "Advances in the Chemistry of Heteroorganic Compounds"
  • Place of Presentation: Lodz, Poland
  • Year and Date: 2010-11-19
• [Presentation] Organosulfur Compounds in Acyclic Stereoselection (2010)
  • Author(s): Takeshi Takeda
  • Organizer: XII National Symposium "Advances in the Chemistry of Heteroorganic Compounds"
  • Place of Presentation: Lodz, Poland 招待講演
  • Year and Date: 2010-11-19
• [Presentation] Organosulfur Compounds in Acyclic Stereoselection (2010)
  • Author(s): Takeshi Takeda
  • Organizer: Xth International Symposium on Selected Problems of Chemistry of Acyclic and Cyclic Heteroorganic Compounds
  • Place of Presentation: Czestochowa, Poland
  • Year and Date: 2010-11-18
• [Presentation] Organosulfur Compounds in Acyclic Stereoselection (2010)
  • Author(s): Takeshi Takeda
  • Organizer: Xth International Symposium on Selected Problems of Chemistry of Acyclic and Cyclic Heteroorganic Compounds
  • Place of Presentation: Czestochowa, Poland 招待講演
  • Year and Date: 2010-11-18
• [Presentation] Highly Stereoselective Construction of Multiple Stereogenic Centers Using Allylic Sulfides (2010)
  • Author(s): Takeshi Takeda
  • Organizer: 24th International Symposium on the Organic Chemistry of Sulfur
  • Place of Presentation: Florence, Italy
  • Year and Date: 2010-07-27
• [Presentation] Construction of arrays of stereogenic centers by the reactions of allyl-and allenyltitanocenes with ketones (2010)
  • Author(s): Takeshi Takeda
  • Organizer: The 6th Asian-European Symposium on Metal-Mediated Reactions
  • Place of Presentation: Singapore
  • Year and Date: 2010-06-08
• [Presentation] Construction of arrays of stereogenic centers by the reactions of allyl-and alienyltitanocenes with ketones (2010)
  • Author(s): Takeshi Takeda
  • Organizer: The 6th Asian-European Symposium on Metal-Mediated Reactions
  • Place of Presentation: Singapore 招待講演
  • Year and Date: 2010-06-08
• [Presentation] Organic Synthesis via Formation of Titanacyclobutenes (2009)
  • Author(s): Takeshi Takeda
  • Organizer: 15^<th> IUPAC International Symposium on Organometallic Chemistry Directed Toward Organic Synthesis
  • Place of Presentation: Glasgow, UK
  • Year and Date: 2009-07-27
• [Book] Organometallic complexes of titanium(update 2011) (2011)
  • Author(s): T. Takeda, A. Tsubouchi, Georg Thieme Verlag
  • Publisher: Science of Synthesis
• [Book] Organometallic complexes of titanium (update 2011), Science of Synthesis, Knowledge Updates (2011)
  • Author(s): T.Takeda, A.Tsubouchi
  • Total Pages: 36
  • Publisher: Georg Thieme Verlag