Development of Rhenium-Catalyzed Synthetic Organic Reactions

• Project/Area Number: 18350019
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Organic chemistry
• Research Institution: Tokyo Institute of Technology
• Principal Investigator: KUSAMA Hiroyuki Tokyo Institute of Technology, 大学院・理工学研究科, 准教授 (30242100)
• Project Period (FY): 2006 – 2008
• Project Status: Completed (Fiscal Year 2008)
• Budget Amount: ¥16,920,000 (Direct Cost: ¥14,400,000、Indirect Cost: ¥2,520,000); Fiscal Year 2008: ¥5,460,000 (Direct Cost: ¥4,200,000、Indirect Cost: ¥1,260,000); Fiscal Year 2007: ¥5,460,000 (Direct Cost: ¥4,200,000、Indirect Cost: ¥1,260,000); Fiscal Year 2006: ¥6,000,000 (Direct Cost: ¥6,000,000)
• Keywords: レニウム触媒 / アルキン / 環化反応 / 多環性骨格 / レニウム / 求電子的活性化 / フェノール / 連続環化 / イリド / 1,3-双極子 / 3+2付加環化

Research Abstract

有機合成における触媒として、これまであまり活用されていなかった低原子価レニウムカルボニル化合物が、単純アルキン類の求電子的活性化に有効であることを明らかとし、この性質を利用することで、比較的単純な鎖状化合物から多置換フェノール類、含窒素多環性化合物等の有用環状化合物を効率よく合成できる新規な触媒反応の開発に成功した。

Research Products

• [Journal Article] Gold-Catalyzed Tandem Cyclization of Dienol-Silyl Ethers for the Preparation of Bicyclo[4. 3. 0]nonane Derivatives (2010)
  • Author(s): Hiroyuki Kusama, Yusuke Karibe, Yuji Onizawa, Nobuharu Iwasawa
  • Journal Title: Angew. Chem. Int. Ed. Vol.49 Pages: 4269-4272
  • Peer Reviewed
• [Journal Article] Rhenium(I)-Catalyzed Cyclization of Silyl Enol Ethers Containing a Propargyl Carboxylate Moiety: A Versatile Access to Highly Substituted Phenols (2010)
  • Author(s): Kodai Saito, Yuji Onizawa, Hiroyuki Kusama, Nobuharu Iwasawa
  • Journal Title: Chem. Eur. J. Vol.16 Pages: 4716-4720
  • Peer Reviewed
• [Journal Article] Rhenium(I)-Catalyzed Cyclization of Silyl Enol Ethers Containing a Propargyl Carboxylate Moiety : A Versatile Access to Highly Substituted Phenols (2010)
  • Author(s): K.Saito
  • Journal Title: Chemistry-A European Journal 16(in press)
  • Peer Reviewed
• [Journal Article] Gold-Catalyzed Tandem Cyclization of Dienol-Silyl Ethers for the Preparation of Bicyclo[4.3.0]nonane Derivatives (2010)
  • Author(s): H.Kusama
  • Journal Title: Angewandte Chemie International Edition 49(in press)
  • Peer Reviewed
• [Journal Article] Pt(II)-Catalyzed Intermolecular [3+2] Cycloaddition Reaction of Propadienyl Silyl Ethers and Alkenyl Ethers (2009)
  • Author(s): H.Kusama
  • Journal Title: Journal of the American Chemical Society 131 Pages: 16352-16353
  • Peer Reviewed
• [Journal Article] Rhodium(I)-Catalyzed [4+1] Cycloaddition Reactions of α, β-Unsaturated Imines with Terminal Alkynes for the Preparation of Pyrrole Derivatives (2009)
  • Author(s): A.Mizuno
  • Journal Title: Angewandte Chemie International Edition 48 Pages: 8318-8320
  • Peer Reviewed
• [Journal Article] Theoretical Study of the Cycloaddition Reaction of a Tungsten-Containing Carbonyl Ylide (2009)
  • Author(s): K.Ito
  • Journal Title: Chemistry-A European Journal 15 Pages: 12408-12416
  • Peer Reviewed
• [Journal Article] Synthesis of N-Fused Tricyclic Indoles by a Tandem [1, 2] Stevens-Type Rearrangement/1, 2-Alkyl Migration of Metal-Containing Ammonium Ylides (2008)
  • Author(s): Jun Takaya, Shuji Udagawa, Hiroyuki Kusama, Nobuharu Iwasawa
  • Journal Title: Angew. Chem. Int. Ed. Vol.47 Pages: 4906-4909
  • Peer Reviewed
• [Journal Article] Efficient Control ofπ-Alkyne and Vinylidene Pathways for W(CO)5(L)-Catalyzed Synthesis of Two Types of Nitrogen-Containing Bicyclic Compounds (2008)
  • Author(s): Yuji Onizawa, Hiroyuki Kusama, Nobuharu Iwasawa
  • Journal Title: J. Am. Chem. Soc. Vol.130 Pages: 802-803
  • Peer Reviewed
• [Journal Article] Platinum(II)-Catalyzed Reaction of γ,δ-Ynones with Alkenes for the Construction of 8-Oxabicyclo [3.2.1] octane Skeletons: Generation of Platinum-Containing Carbonyl Ylides from Acyclic Precursors (2008)
  • Author(s): H. Kusama, K. Ishida, H. Funami, N. Iwasawa
  • Journal Title: Angewandte Chemie International Edition 47(in press)
  • Peer Reviewed
• [Journal Article] New Route to N-fused Tricyclic Indoles via Tandem [1,2]-Stevens-type Rearrangement/1,2-Alkyl Migration of Metal-Containing Ammonium Ylide (2008)
  • Author(s): J. Takaya, S. Udagawa, H. Kusama, N. Iwasawa
  • Journal Title: Angewandte Chemie International Edition 47(in press)
  • Peer Reviewed
• [Journal Article] Efficient Control of π-Alkyne and Vinylidene Complex Pathways for the W(CO)_5 (L)-Catalyzed Synthesis of Two Types of Nitrogen-Containing Bicyclic Compounds (2008)
  • Author(s): Y. Onizawa, H. Kusama, N. Iwasawa
  • Journal Title: Journal of the American Chemical Society 130 Pages: 802-803
  • Peer Reviewed
• [Journal Article] Synthesis of Naphthalene Derivatives through Platinum(II)-Catalyzed Reaction of 2-Alkynylbenzoates with Vinyl Ethers (2007)
  • Author(s): H. Kusama, H. Funami, N. Iwasawa
  • Journal Title: Synthesis 1 Pages: 2014-2024
  • Peer Reviewed
• [Journal Article] W(CO)5(L)-Catalyzed Tandem Intramolecular Cyclopropanation / Cope Rearrangement for the Stereoselective Construction of Bicyclo[5. 3. 0]decane Framework (2006)
  • Author(s): Hiroyuki Kusama, Yuji Onizawa, Nobuharu Iwasawa
  • Journal Title: J. Am. Chem. Soc. Vol.128 Pages: 16500-16501
  • Peer Reviewed
• [Journal Article] Pt(II)-or Au(III)-Catalyzed [3+2] Cycloaddition of Metal-Containing Azomethine Ylides: Highly Efficient Synthesis of Mitosene Skeleton (2006)
  • Author(s): Hiroyuki Kusama, Yuichi Miyashita, Jun Takaya, Nobuharu Iwasawa
  • Journal Title: Org. Lett. Vol.8 Pages: 289-292
  • Peer Reviewed
• [Journal Article] Pt(II)- or Au(III)-Catalyzed [3+2] Cycloaddition of Metal-Containing Azomethine Ylides : Highly Efficient Synthesis of Mitosene Skeleton (2006)
  • Author(s): Hiroyuki Kusama
  • Journal Title: Organic Letters 8 Pages: 289-289
• [Journal Article] Intermolecular 1,5-Dipolar Cycloaddition Reaction of Tungsten-Containing Vinyl-Azomethine Ylides Leading to Seven-Membered Heterocycles (2006)
  • Author(s): Hiroyuki Kusama
  • Journal Title: Organic Letters 8 Pages: 895-895
• [Journal Article] Synthesis of Isochromene Derivatives by 1,6-Addition of Nucleophiles to Benzopyranylidenetungsten Complex (2006)
  • Author(s): Hiroyuki Kusama
  • Journal Title: Organic Letters 8 Pages: 1077-1077
• [Journal Article] W(CO)_5(L)-Catalyzed Tandem Intramolecular Cyclopropanation / Cope Rearrangement for the Stereoselective Construction of Bicyclo[5.3.0]decane Framework (2006)
  • Author(s): Hiroyuki Kusama
  • Journal Title: Journal of the American Chemical Society 128 Pages: 16500-16500
• [Journal Article] Synthetic Studies and Mechanistic Insight in W(CO)5(L)-Catalyzed Stereoselective Construction of Functionalized Bicyclo[5. 3. 0]-decane Framework
  • Author(s): Yuji Onizawa, Masahiro Hara, Takuya Hashimoto, Hiroyuki Kusama, Nobuharu Iwasawa
  • Journal Title: Chem. Eur. J. (印刷中)
  • Peer Reviewed
• [Presentation] 金属含有イリドを活性種とする環状骨格構築法 (2009)
  • Author(s): 草間博之
  • Organizer: 平成21年度有機合成化学講習会
  • Place of Presentation: 東京
  • Year and Date: 2009-11-19
• [Presentation] 金属含有イリドを活性種とする環状骨格構築法 (2009)
  • Author(s): 草間博之
  • Organizer: 平成21年度後期有機合成化学講習会
  • Place of Presentation: 東京
  • Year and Date: 2009-11-19
• [Presentation] レニウム触媒を用いるシリルエノールエーテル部位を有するプロパルギルエステル誘導体からの多置換フェノール合成 (2009)
  • Author(s): 齊藤巧泰、鬼澤裕二、草間博之、岩澤伸治
  • Organizer: 第96回有機合成シンポジウム
  • Place of Presentation: 東京
  • Year and Date: 2009-11-06
• [Presentation] レニウム(I)触媒によるジエンーイン類の環化反応:含窒素環状化合物の選択的合成 (2009)
  • Author(s): 苅部雄輔、今井理恵、鬼澤裕二、草間博之、岩澤伸治
  • Organizer: 第56回有機金属化学討論会
  • Place of Presentation: 京都
  • Year and Date: 2009-09-10
• [Presentation] レニウム触媒によるジエンーイン類の環化反応:含窒素環状化合物の選択的合成 (2009)
  • Author(s): 苅部雄輔
  • Organizer: 第56回有機金属化学討論会
  • Place of Presentation: 京都
  • Year and Date: 2009-09-10
• [Presentation] [3+2]-Cycloaddition of Platinum-Containing Carbonyl Ylides Derived from Linear γ, δ-Ynones (2009)
  • Author(s): Kento Ishida
  • Organizer: 15th IUPAC Symposium on Organometallic Chemistry Directed Towards Organic Synthesis(OMCOS15)
  • Place of Presentation: Glasgow
  • Year and Date: 2009-07-26
• [Presentation] 白金含有カルボニルイリドを活性種とする多環性骨格構築法 (2009)
  • Author(s): 渡辺英一
  • Organizer: 第95回有機合成シンポジウム
  • Place of Presentation: 東京
  • Year and Date: 2009-06-10
• [Presentation] レニウム触媒を用いるシリルエノールエーテル部位を有するプロパルギルエステル誘導体からの多置換フェノールの合成 (2009)
  • Author(s): 齊藤巧泰、鬼澤裕二、草間博之、岩澤伸治
  • Organizer: 日本化学会第89春季年会
  • Place of Presentation: 千葉
  • Year and Date: 2009-03-27
• [Presentation] タングステン(0)触媒を用いるトリエンイン類の連続環化反応に基づくビシクロ[5. 3. 0]デカン誘導体の立体選択的合成 (2009)
  • Author(s): 鬼澤裕二、草間博之、岩澤伸治
  • Organizer: 日本化学会第89春季年会
  • Place of Presentation: 千葉
  • Year and Date: 2009-03-27
• [Presentation] タングステン(0)触媒を用いるトリエンイン類の連続環化反応に基づくビシクロ[5.3.0]デカン誘導体の立体選択的合成 (2009)
  • Author(s): 鬼澤裕二
  • Organizer: 日本化学会第89春季年会
  • Place of Presentation: 千葉
  • Year and Date: 2009-03-27
• [Presentation] Platinum(II)-Catalyzed Reaction of γ, δ-Ynones with Alkenes for the Construction of 8-Oxabicyclo[3.2.1]octane Skeletons (2008)
  • Author(s): 草間博之
  • Organizer: The 3^<rd> International Conference on Cutting-edge Organic Chemistry
  • Place of Presentation: Hangzhou(China)
  • Year and Date: 2008-10-20
• [Presentation] 遷移金属触媒の特性を活かした新規な連続的環形成手法 (2008)
  • Author(s): 草間博之
  • Organizer: 平成20年度若手研究者のためのセミナー
  • Place of Presentation: 名古屋
  • Year and Date: 2008-07-25
• [Presentation] タングステン触媒を用いた連続環化反応に基づく多官能性ビシクロ[5. 3. 0]デカン誘導体の合成 (2008)
  • Author(s): 原雅寛、鬼澤裕二、草間博之、岩澤伸治
  • Organizer: 日本化学会第88春季年会
  • Place of Presentation: 東京
  • Year and Date: 2008-03-29
• [Presentation] レニウム(I)触媒を用いるジエンーイン類の環化反応に基づく含窒素環状化合物の合成 (2008)
  • Author(s): 今井理恵
  • Organizer: 日本化学会第88春季年会
  • Place of Presentation: 東京
  • Year and Date: 2008-03-29
• [Presentation] レニウム(I)触媒を用いるジエン-イン類の環化反応に基づく含窒素環状化合物の合成 (2008)
  • Author(s): 今井理恵、苅部雄輔、鬼澤裕二、草間博之、岩澤伸治
  • Organizer: 日本化学会第88春季年会
  • Place of Presentation: 東京
  • Year and Date: 2008-03-28
• [Presentation] タングステン触媒を用いる含窒素二環性化合物の選択的合成:アルキンπ錯体及びビニリデン錯体間の動的反応制御 (2007)
  • Author(s): 鬼澤裕二、草間博之、岩澤伸治
  • Organizer: 第54回有機金属化学討論会
  • Place of Presentation: 広島
  • Year and Date: 2007-10-28
• [Presentation] タングステン含有アンモニウムイリドの生成と反応 (2007)
  • Author(s): 宇田川秀二、鷹谷絢、草間博之、岩澤伸治
  • Organizer: 第54回有機金属化学討論会
  • Place of Presentation: 広島
  • Year and Date: 2007-10-27
• [Presentation] 金属含有イリドを活性種とする付加環化反応 (2007)
  • Author(s): 草間博之
  • Organizer: 第57回錯体化学討論会
  • Place of Presentation: 名古屋
  • Year and Date: 2007-09-25
• [Presentation] 金属含有アゾメチンイリドを活性種とする多官能性三環性インドールの合成 (2007)
  • Author(s): 内田雅子、原雅寛、宮下佑一、草間博之、岩澤伸治
  • Organizer: 第24回有機合成化学セミナー
  • Place of Presentation: 淡路
  • Year and Date: 2007-09-23
• [Presentation] Novel Method for Construction of Polycyclic Compounds Utilizing Transition Metal- Containing Ylides (2007)
  • Author(s): Hiroyuki Kusama, Yuichi Miyashita, Yasuo Suzuki, Jun Takaya, Nobuharu Iwasawa
  • Organizer: The 2nd International Conference on Cutting-edge Organic Chemistry
  • Place of Presentation: Busan (Korea)
  • Year and Date: 2007-09-04
• [Presentation] Novel Method for Construction of Polycyclic Compounds Utilizing Transition Metal-Containing Ylides (2007)
  • Author(s): Hiroyuki Kusama
  • Organizer: The 2nd International Conference on Cutting-edge Organi c Chemistry
  • Place of Presentation: Busan(Korea)
  • Year and Date: 2007-09-04
• [Presentation] Gold-Catalyzed Tandem Cyclization of Dienynes for the Preparation of Bicyclo[4. 3. 0]nonane Derivatives (2007)
  • Author(s): Yusuke Karibe, Yuji Onizawa, Hiroyuki Kusama, Nobuharu Iwasawa
  • Organizer: 14th IUPAC Symposium on Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS14)
  • Place of Presentation: Nara
  • Year and Date: 2007-08-03
• [Presentation] W(CO)5(L)-Catalyzed Formation of Aza-azomethine Ylides and Subsequent [3+2]-Cycloaddition Reactions with Olefins (2007)
  • Author(s): Antoine Grandmarre, Hiroyuki Kusama, Nobuharu Iwasawa
  • Organizer: 4th IUPAC Symposium on Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS14)
  • Place of Presentation: Nara
  • Year and Date: 2007-08-03
• [Presentation] W(CO)_5(L)-Catalyzed Formation of Aza-azomethine Ylides and Subsequent [3+2]-Cycloaddition Reactions with Olefins (2007)
  • Author(s): Antoine Grandmarre
  • Organizer: 14th IUPAC Symposium on Organometallic Chemistry Directed Towards Organic Synthesis
  • Place of Presentation: 奈良
  • Year and Date: 2007-08-03
• [Presentation] Gold-Catalyzed Tandem Cyclization of Dienynes for the Preparation of Bicyclo[4.3.0]nonane Derivatives (2007)
  • Author(s): Yusuke Karibe
  • Organizer: 14th IUPAC Symposium on Organometallic Chemistry Directed Towards Organic Synthesis
  • Place of Presentation: 奈良
  • Year and Date: 2007-08-03
• [Presentation] [3+2]-Cycloaddition of Platinum-Containing Carbonyl Ylides Derived from Linear γ,δ-Y nones (2007)
  • Author(s): Kento Ishida
  • Organizer: 14th IUPAC Symposium on Organometallic Chemistry Directed Towards Organic Synthesis
  • Place of Presentation: 奈良
  • Year and Date: 2007-08-03
• [Presentation] 遷移金属化合物の特性を活かした触媒的多環性骨格構築手法 (2007)
  • Author(s): 草間博之
  • Organizer: 第42回天然物化学談話会
  • Place of Presentation: 仙台
  • Year and Date: 2007-07-11
• [Presentation] 金触媒によるジエンーイン類の連続環化反応を利用するビシクロ[4. 3. 0]ノナン誘導体の合成 (2007)
  • Author(s): 苅部雄輔、鬼澤裕二、草間博之、岩澤伸治
  • Organizer: 日本化学会第87春季年会
  • Place of Presentation: 大阪
  • Year and Date: 2007-03-26
• [Presentation] タングステン含有アンモニウムイリドの生成と反応 (2007)
  • Author(s): 宇田川秀二、鷹谷絢、草間博之、岩澤伸治
  • Organizer: 日本化学会第87春季年会
  • Place of Presentation: 大阪
  • Year and Date: 2007-03-26
• [Presentation] タングステン(0)触媒によるジエンーイン類の連続環化に基づく二環性化合物の選択的合成 (2007)
  • Author(s): 鬼澤裕二、草間博之、岩澤伸治
  • Organizer: 日本化学会第87春季年会
  • Place of Presentation: 大阪
  • Year and Date: 2007-03-26
• [Presentation] シロキシジエン部位を有するアルキン類の連続環化反応を利用する多環性炭素骨格構築法の開発 (2006)
  • Author(s): 鬼澤裕二、山辺北斗、草間博之、岩澤伸治
  • Organizer: 第90回有機合成シンポジウム
  • Place of Presentation: 東京
  • Year and Date: 2006-11-09
• [Presentation] 遷移金属含有イリド種を経由する環状骨格構築手法 (2006)
  • Author(s): 草間博之
  • Organizer: 第23回有機合成化学セミナー
  • Place of Presentation: 函館
  • Year and Date: 2006-09-13
• [Presentation] Efficient Synthesis of Pyrrolo[1, 2-a]indole Derivatives Based on [3+2] Cycloaddition of Transition Metal- Containing Azomethine Ylides (2006)
  • Author(s): Hiroyuki Kusama, Yuichi Miyashita, Jun Takaya, Nobuharu Iwasawa
  • Organizer: IUPAC International Conference on Biodiversity and Natural Products (ICOB-5 & ISCNP-25)
  • Place of Presentation: Kyoto
  • Year and Date: 2006-07-23