Development of Catalytic Reactions involving Late Transition-metal Vinylidene Species Bearing Hard Ligands

• Project/Area Number: 24350050
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Partial Multi-year Fund
• Section: 一般
• Research Field: Synthetic chemistry
• Research Institution: Keio University
• Principal Investigator: Kakiuchi Fumitoshi 慶應義塾大学, 理工学部, 教授 (70252591)
• Co-Investigator(Kenkyū-buntansha): Kochi Takuya 慶應義塾大学, 理工学部, 専任講師 (70396779)
• Project Period (FY): 2012-04-01 – 2016-03-31
• Project Status: Completed (Fiscal Year 2015)
• Budget Amount: ¥18,720,000 (Direct Cost: ¥14,400,000、Indirect Cost: ¥4,320,000); Fiscal Year 2014: ¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000); Fiscal Year 2013: ¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000); Fiscal Year 2012: ¥10,400,000 (Direct Cost: ¥8,000,000、Indirect Cost: ¥2,400,000)
• Keywords: キノリノラト錯体 / ロジウム / ビニリデン錯体 / 末端アルキン / シクロブテン類 / シクロペンテン類 / アルキン二量化 / 求核攻撃 / キノリノラート / アミノカルベン / ホスフィン / ヒドロアミノ化 / キノリノラト / ビニリデン / PNO三座配位子 / 二核ロジウム錯体 / キノリノラト配位子 / ロジウム触媒 / 末端アセチレン / 活性メチレン化合物 / アミド化合物

Outline of Final Research Achievements

Developments of new catalytic reactions using rhodium-quinolinolato complexes as catalysts have been investigated. We have developed the [Rh(Q)(cod)]-catalyzed 2:1 coupling reaction of terminal alkyne and active methylene compounds leading to cyclopentene derivatives. We found that the coupling of aliphatic alkynes with alkyl acrylates gave cyclobutene derivatives in regioselective manner in high yields. In addition, we synthesized PNO tridentate ligands bearing diphenylphosphinomethylene group at 2-position of the quinolinolate moiety and prepared new types of rhodium complexes having this PNO tridentate ligand.

Research Products

• [Journal Article] Palladium-Catalyzed Regioselective Homocoupling of Arenes Using Anodic Oxidation: Formal Electrolysis of Aromatic Carbon-Hydrogen Bonds (2014)
  • Author(s): 齋藤文登、相磯紘子、河内卓彌、垣内史敏
  • Journal Title: Organometallics Volume: 33 Issue: 22 Pages: 6704-6707
  • DOI: 10.1021/om500957a
  • Peer Reviewed
• [Journal Article] 3)Ruthenium-Catalyzed Ortho-Selective Aromatic C-H Alkenylation with Alkenyl Carbonates (2014)
  • Author(s): 荻原陽平、河内卓彌、垣内史敏
  • Journal Title: Chem. Lett. Volume: 45 Issue: 5 Pages: 667-669
  • DOI: 10.1246/cl.140006
  • NAID: 130004868092
  • Peer Reviewed
• [Journal Article] 4) Rhodium-Catalyzed Dimerization of Arylacetylenes and Addition of Malonates to 1,3-Enynes (2013)
  • Author(s): 望月克史、酒井一憲、河内卓彌、垣内史敏
  • Journal Title: Synthesis Volume: 45 Issue: 15 Pages: 2088-2092
  • DOI: 10.1055/s-0033-1338471
  • Peer Reviewed
• [Journal Article] Rhodium-Catalyzed Intermolecular ［2+2］Cycloaddition to Terminal Alkynes with Electron-Deficient Alkenes (2013)
  • Author(s): K. Sakai, T. Kochi, F. Kakiuchi
  • Journal Title: Organic Letters Volume: 15 Issue: 5 Pages: 1024-1027
  • DOI: 10.1021/ol303510k
  • Peer Reviewed
• [Presentation] 官能基化された8-キノリノラト配位子をもつロジウム錯体を用いた末端アルキンと第二級アミンの触媒的1:1型および2:1型付加反応 (2016)
  • Author(s): 浜田百絵、望月克史、河内卓彌、垣内史敏
  • Organizer: 日本化学会第96春季年会
  • Place of Presentation: 同志社大学(京都府・京田辺市）
  • Year and Date: 2016-03-24
• [Presentation] キノリノラト－ホスフィン配位子をもつロジウム触媒を用いた末端アルキンの逆マルコフニコフ型ヒドロアミノ化反応とその反応機構に関する研究 (2016)
  • Author(s): 鷹野祥太郎、河内卓彌、垣内史敏
  • Organizer: 日本化学会第96春季年会
  • Place of Presentation: 同志社大学(京都府・京田辺市）
  • Year and Date: 2016-03-24
• [Presentation] キノリノラトロジウム触媒を利用する新規分子変換反応の開発 (2016)
  • Author(s): 垣内史敏
  • Organizer: 第5回戦略的研究基盤形成支援事業シンポジウム
  • Place of Presentation: 慶應義塾大学 （神奈川県・横浜市）
  • Year and Date: 2016-03-14
  • Invited
• [Presentation] Development of New Coupling Reactions Using Quinolinolato-rhodium Catalysts (2016)
  • Author(s): 垣内史敏
  • Organizer: Department Seminar at National University of Singapore
  • Place of Presentation: National University of Singapore (Singapore, Singapore)
  • Year and Date: 2016-03-08
  • Invited
• [Presentation] Syntheses and Reactivities of Phosphine-Quinolinolato Rhodium Complexes: Formation of Vinylidene-Bridged Dirhodium Complexes (2015)
  • Author(s): 鷹野祥太郎、河内卓彌、垣内史敏
  • Organizer: The 2015 International Chemical Congress of Pacific Basin Societies (Pacifichem 2015)
  • Place of Presentation: Honolulu (Hawaii, USA)
  • Year and Date: 2015-12-15
  • Int'l Joint Research
• [Presentation] 2:1 Coupling of Terminal Alkynes with Secondary Amines Catalyzed by Quinolinolato Rhodium Complexes (2015)
  • Author(s): 浜田百絵、望月克史、河内卓彌、垣内史敏
  • Organizer: The 2015 International Chemical Congress of Pacific Basin Societies (Pacifichem 2015)
  • Place of Presentation: Honolulu (Hawaii, USA)
  • Year and Date: 2015-12-15
  • Int'l Joint Research
• [Presentation] キノリノラト－ホスフィン配位子をもつ新規ロジウム錯体の合成、反応性および触媒活性 (2015)
  • Author(s): 鷹野祥太郎、河内卓彌、垣内史敏
  • Organizer: 第70回記念有機合成化学協会関東支部シンポジウム
  • Place of Presentation: 長岡工業高等専門学校 （新潟県・長岡市）
  • Year and Date: 2015-11-21
• [Presentation] Syntheses and Reactivities of Phosphine-Quinolinolato Rhodium Complexes (2015)
  • Author(s): 鷹野祥太郎、河内卓彌、垣内史敏
  • Organizer: the 13th International Kyoto Conference on New Aspects of Organic Chemistry (IKCOC-13)
  • Place of Presentation: the Rihga Royal Hotel Kyoto (京都府・京都市）
  • Year and Date: 2015-11-12
  • Int'l Joint Research
• [Presentation] Syntheses and Reactivities of Novel Rhodium Complexes Bearing Pincer-Type PNO Ligands Containing 8-Quinolinolate and Phosphine Moieties (2015)
  • Author(s): 鷹野祥太郎、河内卓彌、垣内史敏
  • Organizer: International Conference on Green and Sustainable Chemistry (GSC-7) and 4th JACI/GSC Symposium)
  • Place of Presentation: 一橋大学一橋講堂 (東京都・千代田区）
  • Year and Date: 2015-07-05
  • Int'l Joint Research
• [Presentation] (8-Quinolinolato)rhodium-catalyzed Coupling Reactions Using Terminal Alkynes (2014)
  • Author(s): 垣内史敏
  • Organizer: 26th International Conference on Organometallic Chemistry
  • Place of Presentation: ロイトンホテル (北海道、札幌市、北区)
  • Year and Date: 2014-07-13 – 2014-07-18
  • Invited
• [Presentation] (Quinolinolato)rhodium-catalyzed Coupling Reactions Using Terminal Alkynes (2014)
  • Author(s): 垣内史敏
  • Organizer: University of Bourgogne Symposium
  • Place of Presentation: Dijon (France)
  • Year and Date: 2014-07-04
  • Invited
• [Presentation] 8-キノリノラトロジウム触媒を用いた末端アルキンの二量化反応および1,3-エンインへの活性メチレン化合物の付加反応 (2013)
  • Author(s): 望月克史、河内卓彌、垣内史敏
  • 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
  • Year and Date: 2013-03-23
• [Presentation] 8-キノリノラトロジウム触媒を用いた末端アルキンと電子不足アルケンの[2+2]環化付加反応によるシクロブテン類の合成 (2013)
  • Author(s): 酒井一憲、河内卓彌、垣内史敏
  • 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
  • Year and Date: 2013-03-23
• [Presentation] キノリノラトロジウム錯体を利用した新規触媒反応 (2013)
  • Author(s): 垣内史敏
  • Organizer: 京都大学第1回卓越拠点有機若手ワークショップ
  • Place of Presentation: 京都大学理学研究科(招待講演)
  • Year and Date: 2013-03-07
• [Presentation] (8-Quinolinolato)rhodium-catalyzed Coupling of Terminal Alkynes with Electron-deficient Alkenes (2013)
  • Author(s): 垣内史敏
  • Organizer: 11th International Symposium on Organic Reaction
  • Place of Presentation: 台北、台湾
  • Invited
• [Presentation] (Quinolinolato)rhodium-catalyzed Couplings of Alcohols and Secondary Amines with Terminal Alkynes (2013)
  • Author(s): 垣内史敏
  • Organizer: 15th Asian Chemical Congress
  • Place of Presentation: シンガポール
  • Invited
• [Presentation] ロジウム触媒を用いたアリールアセチレンの選択的二量化と1,3-エンインへのマロン酸エステル類の付加反応 (2013)
  • Author(s): 望月克史、河内卓彌、垣内史敏
  • Organizer: 第2回JACI/GSCシンポジウム
  • Place of Presentation: 大阪
• [Presentation] Synthesis of Cyclobutenes by [2+2]Cycloaddition of Terminal Alkynes with Electron-Deficient Alkenes Using 8-Quinolinolato Rhodium Catalysts (2012)
  • Author(s): 酒井一憲、河内卓彌、垣内史敏
  • Organizer: the Twelfth International Kyoto Conference on New Aspects of Organic Chemistry (IKCOC-12)
  • Place of Presentation: 京都
  • Year and Date: 2012-11-13
• [Presentation] Rhodium-Catalyzed Dimerization of Arylacetylenes and Cascade Additions of Active Methylene Compounds (2012)
  • Author(s): 望月克史、河内卓彌、垣内史敏
  • Organizer: the Twelfth International Kyoto Conference on New Aspects of Organic Chemistry (IKCOC-12)
  • Place of Presentation: 京都
  • Year and Date: 2012-11-13
• [Presentation] 8-キノリノラトロジウム/ホスフィン触媒による末端アルキンとアミンおよびアルケンの新規付加反応の開発 (2012)
  • Author(s): 酒井一憲、河内卓彌、垣内史敏
  • Organizer: 第59回有機金属化学討論会
  • Place of Presentation: 大阪大学、大阪
  • Year and Date: 2012-09-14
• [Presentation] [2+2]Cycloaddition of Terminal Alkynes with Electron-Deficient Alkenes Catalyzed by 8-Quinolinolato Rhodium Complexes (2012)
  • Author(s): 酒井一憲、河内卓彌、垣内史敏
  • Organizer: the XXV International Conference on Organometallic Chemistry (XXV ICOMC)
  • Place of Presentation: the Lisbon University Campus, Protugal
  • Year and Date: 2012-09-14