Search for new synthetic reactions by the use of transition metal as a reagent and/or a catalyst

• Project/Area Number: 19590012
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Chemical pharmacy
• Research Institution: Showa Pharmaceutical University
• Principal Investigator: HANZAWA Yuji Showa Pharmaceutical University, 薬学部, 教授 (10096688)
• Project Period (FY): 2007 – 2008
• Project Status: Completed (Fiscal Year 2008)
• Budget Amount: ¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000); Fiscal Year 2008: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000); Fiscal Year 2007: ¥3,250,000 (Direct Cost: ¥2,500,000、Indirect Cost: ¥750,000)
• Keywords: 有機化学 / ジルコノセン錯体 / 遷移金属触媒 / 不斉配位子 / エナンチオ選択性 / 複素環合成 / メタセシス反応 / 触媒反応 / 生理活性 / 不斉配立子 / 環形成反応 / 立本選択的反応 / 不斉補助基 / 複素環

Research Abstract

反応活性の低い有機ジルコノセン錯体を化合物合成のための重要な試薬として活用すべく、様々な触媒を用いて、炭素-炭素結合の新規構築法を開発した。特に、生理活性が期待される化合物への反応を触媒存在下に有機ジルコノセン錯体由来の各種置換基の導入を行い、光学活性複素環化合物の新規な構築法を開発した。また、ジルコニウム以外の他の遷移金属触媒を用いる環状化合物の効率のよい触媒的合成法を明らかにすることができた。

Research Products

• [Journal Article] Rhodium(I)-catalyzed synthesis of indoles:amino-Claisen rearrangement of propargyl aniline (2009)
  • Author(s): A. Saito, S. Oda, H. Fukaya, Y. Hanzawa
  • Journal Title: J. Org. Chem 74 Pages: 1517-1524
  • Peer Reviewed
• [Journal Article] Catalytic addition of alkenylzirconocene chloride to 3,4-dihydroisoquinoline and its enantioselective reaction (2009)
  • Author(s): A. Saito, K. Iimura, M. Hayashi, Y. Hanzawa
  • Journal Title: Tetrahedron Lett 50 Pages: 587-589
  • Peer Reviewed
• [Journal Article] Catalytic addition of alkenylzirconocene chloride to 3, 4-dihydroisoquinoline and its enantioselective reaction (2009)
  • Author(s): Saito, A.
  • Journal Title: Terahedon Letters 50 Pages: 587-589
  • Peer Reviewed
• [Journal Article] Rhodium(1)-catalyzed synthesis of lndoles : Amino-Claisen Rearrangement of N-Propargylanilines (2009)
  • Author(s): Saito, A.
  • Journal Title: J. Organic Chemistry 74 Pages: 1517-1524
  • Peer Reviewed
• [Journal Article] Novel one-pot approach to synthesis of indanones through Sb(V)-catalyzed reaction of phenylalkynes with aldehydes (2008)
  • Author(s): A. Saito, M. Umakoshi, N. Yagyu, Y. Hanzawa
  • Journal Title: Org. Lett. 10 Pages: 1783-1785
  • Peer Reviewed
• [Journal Article] Novel One-Pot Approach to Synthesis of Indanones through Sb(V)-Catalyzed Reaction of Phenylalkynes with Aldehydes (2008)
  • Author(s): Saito, A
  • Journal Title: Organic Letters 10 Pages: 1783-1785
  • Peer Reviewed
• [Journal Article] Acylzirconocene chloride: Formation of carbocycles by palladium-catalyzed cascade reaction (2007)
  • Author(s): Y. Hanzawa, Y. Oka, M. Yabe
  • Journal Title: J. Organometallic Chem 692 Pages: 4528-4534
  • Peer Reviewed
• [Journal Article] Rh(I)-catalyzed intramolecular hetero[4+2] cycloaddition of ω-alkenyl-vinyl oximes (2007)
  • Author(s): A. Saito, M. Hironaga, S. Oda, Y. Hanzawa
  • Journal Title: Tetrahedron Lett 48 Pages: 6852-6855
  • Peer Reviewed
• [Journal Article] Rh(I)-catalyzed conjugate addition of alkenylzirconocene chloride: stereoselective formation of carbocycles through cascade reaction (2007)
  • Author(s): Y. Hanzawa, Y. Takebe, A. Saito, A. Kakuuchi, H. Fukaya
  • Journal Title: Tetrahedron Lett 48 Pages: 6471-6474
  • Peer Reviewed
• [Journal Article] Synthesis of tetrahydroisoquinolines and isochromans via Pictet-Spengler reactions catalyzed by Bronsted acid-surfactantcombined catalyst in aqueous media (2007)
  • Author(s): A. Saito, M. Takayama, A. Yamazaki, J. Numaguchi, Y. Hanzawa
  • Journal Title: Tetrahedron 63 Pages: 4039-4047
  • Peer Reviewed
• [Journal Article] Generation and reaction of heteroaromatic zirconocene: synthetic application to polycyclic heterocycles (2007)
  • Author(s): Y. Ikeuchi, T. Saitoh, T. Taguchi, Y. Hanzawa
  • Journal Title: Tetrahedron Lett 48 Pages: 2477-2480
  • Peer Reviewed
• [Journal Article] Pictet-Spengler reactions catalyzed by Bronsted acid-surfactant-combined catalyst in water or aqueous media (2007)
  • Author(s): A. Saito, J. Numaguchi, Y. Hanzawa
  • Journal Title: Tetrahedron Lett 48 Pages: 835-839
  • Peer Reviewed
• [Journal Article] Rh(I)-catalyzed conjugate addition of alkenylzirconocene chloride;ste; stereoselective formation of carbocycles through cascade reaction (2007)
  • Author(s): Hanzawa, Y.
  • Journal Title: Tetrahedron Letters 48 Pages: 6470-6474
  • Peer Reviewed
• [Journal Article] Acylzirconocene chloride:Formation of carbocycles by palladium-catalyzed cascade reaction (2007)
  • Author(s): Hanzawa, Y.
  • Journal Title: J.Organometallic Chem. 692 Pages: 4528-4534
  • Peer Reviewed
• [Journal Article] Synthesis of 2,3-Disubstituted Indoles by a Rh-Catalyzed Aromatic Amino-Claisen Rearrangement of N-propargyl Anilines (2007)
  • Author(s): Saito, A.
  • Journal Title: Angewandte Chem.Int.Ed. 46 Pages: 3931-3933
  • Peer Reviewed
• [Journal Article] Synthesis of 2,3-disubstituted indoles by a rhodium-catalyzed aromatic amino-Claisen rearrangement of N-propargyl anilines
  • Author(s): A. Saito, A. Kanno, Y. Hanzawa
  • Journal Title: Angew. Chem. Int. Ed 46 Pages: 3931-3933
  • Peer Reviewed
• [Presentation] ロジウム錯体を触媒とするアミノクライゼン転位反応における活性種の解析に関する研究 (2009)
  • Author(s): 斉藤亜紀夫
  • Organizer: 日本薬学会第129 年会
  • Place of Presentation: 京都
  • Year and Date: 2009-03-28
• [Presentation] ロジウム触媒を用いるプロパルギルアミン誘導体と1,3-ジケトン化合物からのピロール誘導体の合成 (2009)
  • Author(s): 飯村康一
  • Organizer: 日本薬学会第129 年会
  • Place of Presentation: 京都
  • Year and Date: 2009-03-28
• [Presentation] アルキン-カルボニルメタセシス反応を利用する1段階2,3-dihydro-quinoline-4-oneの合成 (2009)
  • Author(s): 河西 潤
  • Organizer: 日本薬学会第129 年会
  • Place of Presentation: 京都
  • Year and Date: 2009-03-27
• [Presentation] アルケニルジルコノセン錯体を求核試薬とする複素環化合物への付加反応 (2008)
  • Author(s): 飯村康一
  • Organizer: 第34 回反応と合成の進歩シンポジウム
  • Place of Presentation: 京都
  • Year and Date: 2008-11-05
• [Presentation] アルキン-カルボニルメタセシス反応を利用する1段階インダノン合成 (2008)
  • Author(s): 河西 潤
  • Organizer: 第34 回反応と合成の進歩シンポジウム
  • Place of Presentation: 京都
  • Year and Date: 2008-11-04
• [Presentation] One-pot synthesis of 2,3-disubstituted indanones from phenylalkynes and aldehydes (2008)
  • Author(s): Akio Saito
  • Organizer: 236^<th> ACS National Meeting
  • Place of Presentation: Philadelphia, USA
  • Year and Date: 2008-08-17
• [Presentation] ロジウム触媒を用いたアミノクライゼン転位反応を基盤とするインドール合成 (2008)
  • Author(s): 小田祥子
  • Organizer: 日本薬学会第128 年会
  • Place of Presentation: 横浜
  • Year and Date: 2008-03-26
• [Presentation] Rhodium-catalyzed synthesis of indole compounds from N-proparugyl anilines or the related compounds (2008)
  • Author(s): Shoko Oda
  • Organizer: Pan-Pacific International Partnership Conference on Pharmaceutical and Life Sciences
  • Place of Presentation: Nagoya, Japan
  • Year and Date: 2008-02-23
• [Presentation] フェニルアルキンとアルデヒドとのカップリング-環化反応:1段階インダノン合成 (2008)
  • Author(s): 齊藤 亜紀夫
  • Organizer: 第6回次世代を担う有機化学シンポジウム
  • Place of Presentation: 東京
• [Presentation] アルキン-カルボニルメタセシス反応を経由する1段階インダノン合成 (2008)
  • Author(s): 河西 潤
  • Organizer: 第34回反応と合成の進歩シンポジウム
  • Place of Presentation: 京都
• [Presentation] アルケニルジルコノセン錯体を求核試薬とする複素環化合物への付加反応 (2008)
  • Author(s): 飯村康一
  • Organizer: 第34回反応と合成の進歩シンポジウム
  • Place of Presentation: 京都
• [Presentation] ロジウム触媒を用いたアミノクライゼン転位反応を基盤とするインドール合成 (2008)
  • Author(s): 小田祥子
  • Organizer: 日本薬学会第128年会
  • Place of Presentation: 横浜
• [Presentation] アルケニルジルコノセン錯体を用いた含窒素複素環化合物への求核付加反応 (2008)
  • Author(s): 林 未来
  • Organizer: 日本薬学会第128年会
  • Place of Presentation: 横浜
• [Presentation] フェニルアルキン誘導体とアルデヒド類との分子間カップリング反応による1段階インタノン合成 (2008)
  • Author(s): 斉藤亜紀夫
  • Organizer: 日本薬学会第128年会
  • Place of Presentation: 横浜
• [Presentation] One-pot synthesis of 2, 3-disubstituted indanones from phenylalkynes and aldehydes (2008)
  • Author(s): A. Saito
  • Organizer: 236^<th> ACS National Meeting
  • Place of Presentation: Philadelphia
• [Presentation] ロジウム錯体を触媒とするインドール合成 (2007)
  • Author(s): 小田 祥子
  • Organizer: 第33回反応と合成の進歩シンポジウム
  • Place of Presentation: 長崎
  • Year and Date: 2007-11-06
• [Presentation] ロジウム錯体を触媒とするインドール合成 (2007)
  • Author(s): 斉藤亜紀夫
  • Organizer: 第33 回反応の合成の進歩シンポジウム
  • Place of Presentation: 長崎
  • Year and Date: 2007-11-05
• [Presentation] アルケニルジルコノセンクロリド錯体を用いる求核的アルケニル化 (2007)
  • Author(s): 林 未来
  • Organizer: 第51 回日本薬学会関東支部会
  • Year and Date: 2007-10-16
• [Presentation] アルケニルジルコノセンクロリド錯体を用いる求核的アルケニル化 (2007)
  • Author(s): 林 未来
  • Organizer: 第51回日本薬学会 関東支部大会
  • Place of Presentation: 東京
  • Year and Date: 2007-10-06
• [Presentation] Transition metal-catalyzed reaction of N-propargyl anilines: Synthesis of heteroaromatic compounds (2007)
  • Author(s): Yuji Hanzawa
  • Organizer: 234^<th> ACS National Meeting
  • Place of Presentation: Boston, USA
  • Year and Date: 2007-08-19
• [Presentation] Transition meta-catalyzed reaction of N-propargyl anilines:Synthesis of heteroaromatic compounds (2007)
  • Author(s): Hanzawa, Y.
  • Organizer: 234th American Chemical Society
  • Place of Presentation: Boston
  • Year and Date: 2007-08-19
• [Presentation] Synthesis of 2,3di- substituted Indoles by cationic rhodium- catalyzed aromatic amino-Claisen rearrangement of N-propargyl anilines (2007)
  • Author(s): Akio Saito
  • Organizer: 14^<th> IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis
  • Place of Presentation: Nara, Japan
  • Year and Date: 2007-08-02
• [Remarks]
  • URL: http://www.shoyaku.ac.jp/labosite/hannou/index.html
• [Remarks]
  • URL: http://www.shoyaku.ac.jp/labosite/hannou/index.html