Development of Cleavage Reactions of C-O and N-S Bonds Promoted by Novel Low-Valent Titanium Reagents and Their Synthetic Applications

• Project/Area Number: 22550103
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Synthetic chemistry
• Research Institution: Kanagawa University
• Principal Investigator: OKAMOTO Sentaro 神奈川大学, 工学部, 教授 (00201989)
• Project Period (FY): 2010 – 2012
• Project Status: Completed (Fiscal Year 2012)
• Budget Amount: ¥4,810,000 (Direct Cost: ¥3,700,000、Indirect Cost: ¥1,110,000); Fiscal Year 2012: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000); Fiscal Year 2011: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000); Fiscal Year 2010: ¥2,210,000 (Direct Cost: ¥1,700,000、Indirect Cost: ¥510,000)
• Keywords: 選択的合成・反応 / 低原子価チタニウム / 有機化学 / 有機合成化学 / 低原子価チタン反応剤 / 結合解裂 / チタナトラン / オキセタン / エポキシド / ラジカル反応 / 脱保護法 / スルホンアミド

Research Abstract

In this research on low-valent titanium-promoted C-O and N-S bondcleavage reactions, radical reductive ring-opening reaction of epoxides includingstereoselective reactions and S-N bond cleavage of sulfonamides and sulfonylesters havebeen developed. In addition, novel valence-selective generation of low-valent titanium,radical ring-opening of oxetanes and reductive McMurry-type coupling reaction have beendiscovered.

Research Products

• [Journal Article] Non-Cp Titanium Alkoxide-Based Homolytic Ring-Opening of Epoxides by An Intramolecular Hydrogen Abstraction in beta-Titanoxy Radical Intermediates (2011)
  • Author(s): Tsuyoshi Kawaji, Noriaki Shoji, Kenji Miyashita, Sentaro Okamoto
  • Journal Title: Chemical Communications Volume: Vol.47 Pages: 7857-7859
  • Peer Reviewed
• [Journal Article] Ti(O-i-Pr)4/Me3SiCl/Mg-Mediated Reductive Cleavage of Sulfonamides and Sulfonates To Amines and Alcohols (2011)
  • Author(s): Noriaki Shohji, Tsuyoshi Kawaji, SentaroOkamoto
  • Journal Title: Organic Letters Volume: Vol. 13 Pages: 2626-2629
  • Peer Reviewed
• [Journal Article] Non-Cp Titanium Alkoxide-Based Homolytic Ring-Opening of Epoxides by An Intramolecular Hydrogen Abstraction in β-Titanoxy Radical Intermediates (2011)
  • Author(s): Tsuyoshi Kawaji, Sentaro Okamoto, 他
  • Journal Title: Chemical Communications Volume: 47 Issue: 27 Pages: 7857-7859
  • DOI: 10.1039/c1cc12969d
  • Peer Reviewed
• [Journal Article] Ti(O-i-Pr)_4/Me_3SiCl/Mg-Mediated Reductive Cleavage of Sulfonamides and Sulfonates To Amines and Alcohols (2011)
  • Author(s): Noriaki Shohji, Tsuyoshi Kawaji, Sentaro Okamoto
  • Journal Title: Organic Letters Volume: 13 Pages: 2626-2629
  • Peer Reviewed
• [Journal Article] McMurry coupling of aryl aldehydes and imino pinacol coupling mediated byTi(O-i-Pr)4/MeSiCl/Mg reagent (2010)
  • Author(s): Sentaro Okamoto, Jing-Qian He, Chihaya Ohno, Yuhji Oh-iwa, and Yuhki Kawaguchi
  • Journal Title: Tetrahedron Letters Volume: Vol. 51 Pages: 387-390
  • Peer Reviewed
• [Presentation] Titanatraneを触媒とするオキセタンのラジカル還元 (2013)
  • Author(s): 竹腰直人・宮下賢司・松野千加士・岡本専太郎
  • Organizer: 日本化学会第93春季年会
  • Place of Presentation: 滋賀
• [Presentation] 低原子価チタン反応剤によるオキセタンのラジカル還元反応 (2012)
  • Author(s): 竹腰直人, 正路則朗, 松野千加士, 岡本専太郎
  • Organizer: 日本化学会第92春季年会
  • Place of Presentation: 神奈川,川崎市,慶応義塾大学
  • Year and Date: 2012-03-27
• [Presentation] 低原子価チタン反応剤によるオキセタンのラジカル還元反応 (2012)
  • Author(s): 竹腰直人・正路則朗・松野千加士・岡本専太郎
  • Organizer: 日本化学会第92春季年会
  • Place of Presentation: 神奈川
• [Presentation] Ti(O-i-Pr)_4/Me_3SiCl/Mgを用いる合成反応の開発 (2011)
  • Author(s): 正路則明, 河治健, 岡本専太郎
  • Organizer: 第100回有機合成シンポジウム
  • Place of Presentation: 東京,早稲田大学
  • Year and Date: 2011-11-11
• [Presentation] 低原子価チタンによるエポキシドの還元反応とその機構 (2011)
  • Author(s): 相坂真仁・宮下賢司・正路則朗・河治健・岡本専太郎
  • Organizer: 日本化学会第91春季年会
  • Place of Presentation: 横浜・神奈川大学
  • Year and Date: 2011-03-28
• [Presentation] 低原子価チタンによるスルホンアミドの還元的解裂反応とその機構 (2011)
  • Author(s): 正路規朗・河治健・岡本専太郎
  • Organizer: 日本化学会第91春季年会
  • Place of Presentation: 横浜・神奈川大学
  • Year and Date: 2011-03-28
• [Presentation] Ti(O-i-Pr)4/MeSiCl/Mgを用いる合成反応の開発 (2011)
  • Author(s): 正路則明・河治健・岡本専太郎
  • Organizer: 第100回有機合成シンポジウム
  • Place of Presentation: 東京
• [Presentation] 低原子価チタンによるスルホンアミドの還元的解裂反応とその機構 (2011)
  • Author(s): 正路則明・河治健・岡本専太郎
  • Organizer: 日本化学会第91春季年会
  • Place of Presentation: 横浜
• [Presentation] 低原子価チタンによるエポキシドの還元反応とその機構 (2011)
  • Author(s): 相坂真仁・宮下賢司・正路則朗・河治健・岡本専太郎
  • Organizer: 日本化学会第91春季年会
  • Place of Presentation: 横浜
• [Presentation] Generation and reactivity of new low valent titanium alkoxides (2010)
  • Author(s): Tsuyoshi Kawaji, Sentaro Okamoto
  • Organizer: 環太平洋化学国際会議
  • Place of Presentation: ハワイ(ホノルル)・コンベンションセンター
  • Year and Date: 2010-12-17
• [Presentation] Ti(O-i-Pr)4/Me3SiCl/Mg-mediated reductive cleavage of sulfonyl amides and esters to amines or alcohols with thiols (2010)
  • Author(s): S. Okamoto, N. Sho-ji, T. Kawaji, C.Matsuno
  • Organizer: 2010 International Chemical Congress of Pacific Basin Societies
  • Place of Presentation: USA, Hawaii
• [Presentation] Ti(II)反応剤によるエンイノール誘導体のメタロエン型環化反応の展開 (2010)
  • Author(s): 長谷川祐介・林直斗・松野千加士・岡本専太郎
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 大阪
• [Presentation] Titanatraneを触媒とするオキセタンのラジカル還元
  • Author(s): 竹腰直人・宮下賢司・松野千加士・ 岡本専太郎
  • Organizer: 日本化学会第93春季年会
  • Place of Presentation: 立命館大学 びわこくさつキャンパス
• [Remarks] 研究室
  • URL: http://apchem2.kanagawa-u.ac.jp/~okamotolab/index.html