Design of metal complexes with organic ligand bearing photo-sensitive moieties and its application to catalytic transformations

• Project/Area Number: 24350068
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Partial Multi-year Fund
• Section: 一般
• Research Field: Functional materials chemistry
• Research Institution: Osaka University
• Principal Investigator: Yasuda Makoto 大阪大学, 工学(系)研究科(研究院), 教授 (40273601)
• Project Period (FY): 2012-04-01 – 2016-03-31
• Project Status: Completed (Fiscal Year 2015)
• Budget Amount: ¥18,980,000 (Direct Cost: ¥14,600,000、Indirect Cost: ¥4,380,000); Fiscal Year 2014: ¥2,210,000 (Direct Cost: ¥1,700,000、Indirect Cost: ¥510,000); Fiscal Year 2013: ¥4,550,000 (Direct Cost: ¥3,500,000、Indirect Cost: ¥1,050,000); Fiscal Year 2012: ¥12,220,000 (Direct Cost: ¥9,400,000、Indirect Cost: ¥2,820,000)
• Keywords: 錯体 / 光反応 / 反応場 / ルイス酸 / 共役 / 有機合成反応

Outline of Final Research Achievements

The boron compounds are abundant but less effective for catalyst. We have synthesized a new boron compounds with cage-shaped organic framework with photo-sensitive moieties. The newly synthesized cage-shaped boron compounds acted as a catalyst for some organic reactions. The selective reaction of aromatic compounds over aliphatic compounds was accomplished due to the pi-pocket moiety around the boron center in the complex. Introduction of benzofuran moiety into cage-shaped borate led to the photo-sensitive catalyst. In fact, irradiation of UV light to the reaction of silly enolate with aldehyde in the presence of the benzofuran-based catalyst made the increased catalytic activity. Irradiation of black-light also increased the yield of the product. The synthesized complexes were fully analyzed by X-ray crystallography and theoretical calculation.

Research Products

• [Journal Article] Photoredox α-Allylation of α-Halocarbonyls with Allylboron Compounds Accelerated by Fluoride Salts under Visible Light Irradiation (2016)
  • Author(s): Itaru Suzuki, Naoto Esumi, and Makoto Yasuda
  • Journal Title: Asian J. Org. Chem. Volume: 5 Issue: 2 Pages: 179-182
  • DOI: 10.1002/ajoc.201500475
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Synthesis, Characterization, and Properties of a Benzofuran-based Cage-shaped Borate: Photo Activation of Lewis Acid Catalysts (2016)
  • Author(s): Akihito Konishi, Ryosuke Yasunaga, Kouji Chiba, and Makoto Yasuda
  • Journal Title: Chem. Commun. Volume: 52 Issue: 16 Pages: 3348-3351
  • DOI: 10.1039/c6cc00291a
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Indium Tribromide Catalyzed Coupling Reaction of Enol Ethers with Silyl Ketene Imines toward Synthesis of ß,γ-Unsaturated Nitriles (2015)
  • Author(s): Yoshihiro Nishimoto, Takashi Nishimura, Makoto Yasuda
  • Journal Title: Chem. Eur. J. Volume: 21 Issue: 50 Pages: 18301-18308
  • DOI: 10.1002/chem.201503414
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Chiral Transfer in the Reaction of Aminoallylic Stannanes with Carbonyls in Two Different Modes using Tin(II) and Indium(III) Halides for the Synthesis of Each Enantiomer (2014)
  • Author(s): Makoto Yasuda, Yoshitaka Nagano, Hiroshi Yunoki, Kensuke Tsuruwa, Akio Baba
  • Journal Title: Organometallics Volume: 33 Issue: 15 Pages: 3924-3927
  • DOI: 10.1021/om500768e
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Gallium Trihalide Catalyzed Sequential Addition of Two Different Carbon Nucleophiles to Esters by Using Silyl Cyanide and Ketene Silyl Acetals (2014)
  • Author(s): Yoshihiro Inamoto, Yuta Kaga, Yoshihiro Nishimoto, Makoto Yasuda, Akio Baba
  • Journal Title: Chemistry - A European Journal Volume: 37 Issue: 37 Pages: 11664-11668
  • DOI: 10.1002/chem.201403734
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] GaBr3-Catalyzed Coupling between α-Iodo Esters with Alkynylstannanes under UV Irradiation (2014)
  • Author(s): Itaru Suzuki, Naoto Esumi, Makoto Yasuda, Akio Baba
  • Journal Title: Chem. Lett. Volume: 44 Issue: 1 Pages: 38-40
  • DOI: 10.1246/cl.140888
  • NAID: 130004699192
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Indium Chloride Catalyzed Alkylative Rearrangement of Propargylic Acetates Using Alkyl Chlorides, Alcohols, and Acetates: Facile Synthesis of α-Alkyl-α,β-Unsaturated Carbonyl Compounds (2014)
  • Author(s): Yoshiharu Onishi, Yoshihiro Nishimoto, Makoto Yasuda, Akio Baba
  • Journal Title: Org. Lett. Volume: 16 Issue: 4 Pages: 1176-1179
  • DOI: 10.1021/ol500046e
  • Peer Reviewed
• [Journal Article] Lithium Phenolates with A Hexagonal-prismatic Li6O6 Core Isolated via A Cage-shaped Tripodal Ligands System : Crystal Structures and Their Behavior in Solution (2012)
  • Author(s): 中島秀人、安田誠、馬場章夫
  • Journal Title: Dalton Trans. Volume: 41 Issue: 22 Pages: 6602-6606
  • DOI: 10.1039/c2dt30266g
  • Peer Reviewed
• [Journal Article] Gallium Tribromide Catalyzed Coupling Reaction of Alkenyl Ethers with Ketene Silyl Acetals (2012)
  • Author(s): Nishimoto, Y.; Ueda, H.; Yasuda, M.; Baba, A
  • Journal Title: Angew. Chem. Int. Ed Volume: 51 Issue: 32 Pages: 8073-8076
  • DOI: 10.1002/anie.201203778
  • Peer Reviewed
• [Journal Article] InCl_3/Me_3SiCl-Catalyzed Direct Michael Addition of Enol Acetates to α,β-Unsaturated Ketones (2012)
  • Author(s): 大西祥晴・米田勇樹・西本能弘・安田 誠・馬場章夫
  • Journal Title: Organic Letter Volume: 14 Issue: 22 Pages: 5788-5791
  • DOI: 10.1021/ol302888k
  • Peer Reviewed
• [Presentation] 金属と炭素の協同作用：芳香族化合物を選択的に見分ける金属触媒の設計 (2015)
  • Author(s): 安田 誠
  • Organizer: 平成27年度有機合成化学北陸セミナー
  • Place of Presentation: 富山観光ホテル
  • Year and Date: 2015-10-02
  • Invited
• [Presentation] Lewis Acids Bearing Cage-Shaped Organic Ligands for Catalysts of Selective Reactions (2015)
  • Author(s): Makoto Yasuda
  • Organizer: Golden Jubilee Chemistry Conference
  • Place of Presentation: NUSS Kent Ridge Guild House, Singapore
  • Year and Date: 2015-08-06
  • Int'l Joint Research / Invited
• [Presentation] 有機骨格による金属錯体設計と触媒利用 (2015)
  • Author(s): 安田 誠
  • Organizer: 第50回有機反応若手の会
  • Place of Presentation: 広島エアポートホテル／フォレストヒルズガーデン
  • Year and Date: 2015-07-29
  • Invited
• [Presentation] インジウム触媒によるα-アルコキシケトンとアルコールの直接カップリング反応 (2015)
  • Author(s): 鈴木 至・川口 奈々・安田 誠
  • Organizer: 日本化学会代95春季年会
  • Place of Presentation: 日本大学（千葉県船橋市）
  • Year and Date: 2015-03-26 – 2015-03-29
• [Presentation] エノール誘導体とシリルケテンアセタールの臭化ガリウム触媒カップリングの反応機構解明 (2015)
  • Author(s): 西本 能弘・喜多 悠二・安田 誠・馬場 章夫
  • Organizer: 日本化学会代95春季年会
  • Place of Presentation: 日本大学（千葉県船橋市）
  • Year and Date: 2015-03-26 – 2015-03-29
• [Presentation] 複素環を骨格に導入したかご型ホウ素錯体の光によるルイス酸性制御 (2015)
  • Author(s): 安永 亮佑・西本 能弘・安田 誠
  • Organizer: 日本化学会代95春季年会
  • Place of Presentation: 日本大学（千葉県船橋市）
  • Year and Date: 2015-03-26 – 2015-03-29
• [Presentation] 有機色素触媒を用いたトリフルオロボラート塩によるα-ハロカルボニル化合物のアリル化反応 (2015)
  • Author(s): 江住 直人・鈴木 至・安田 誠
  • Organizer: 日本化学会代95春季年会
  • Place of Presentation: 日本大学（千葉県船橋市）
  • Year and Date: 2015-03-26 – 2015-03-29
• [Presentation] 分子認識部位を付与したルイス酸開発 (2015)
  • Author(s): 安田 誠
  • Organizer: 新学術領域研究「分子活性化」 第８回公開シンポジウム
  • Place of Presentation: 大阪大学（大阪府豊中市）
  • Year and Date: 2015-01-23 – 2015-01-24
• [Presentation] Cage-Shaped Borates as a Catalysis for Selective Recognition of Aromatic Compounds (2014)
  • Author(s): 安田 誠
  • Organizer: The Ninth International Symposium on Integrated Synthesis
  • Place of Presentation: 夢舞台国際会議場（兵庫県淡路市）
  • Year and Date: 2014-11-14 – 2014-11-15
  • Invited
• [Presentation] Cage-Shaped Borates as a Catalysis for Selective Recognition of Aromatic Compounds (2014)
  • Author(s): Makoto Yasuda
  • Organizer: The Ninth International Symposium on Integrated Synthesis (ISIS-9)
  • Place of Presentation: Awaji Yumebutai International Conference Center, Awaji Island, Hyogo, Japan
  • Year and Date: 2014-11-14
  • Int'l Joint Research / Invited
• [Presentation] Development of GaBr3-Catalyzed Cross Coupling Using Enol Derivatives as Alkenyl Electrophiles (2014)
  • Author(s): Yoshihiro Nishimoto, Yuji Kita, Makoto Yasuda, Akio Baba
  • Organizer: The 2nd International Conference on Organometallics and Catalysis
  • Place of Presentation: 東大寺総合文化センター（奈良県奈良市）
  • Year and Date: 2014-10-26 – 2014-10-29
• [Presentation] Zinc-Catalyzed Coupling of Acetals with Terminal Alkynes: Facile Access to Functionalized Prooargyl Ethers (2014)
  • Author(s): Itaru Suzuki, Makoto Yasuda, Akio Baba
  • Organizer: The 2nd International Conference on Organometallics and Catalysis
  • Place of Presentation: 東大寺総合文化センター（奈良県奈良市）
  • Year and Date: 2014-10-26 – 2014-10-29
• [Presentation] アセタール類と末端アルキンの塩化亜鉛触媒直接カ ップリング反応 (2014)
  • Author(s): 鈴木 至・安田 誠・馬場章夫
  • Organizer: 第4回CSJ化学フェスタ2014
  • Place of Presentation: タワーホール船堀（東京都江戸川区）
  • Year and Date: 2014-10-14 – 2014-10-16
• [Presentation] 可視光酸化還元触媒を用いたアリルホウ素試薬とα-ハロカルボニル化合物のカップリング反応 (2014)
  • Author(s): 江住 直人・鈴木至・安田 誠
  • Organizer: 第4回CSJ化学フェスタ2014
  • Place of Presentation: タワーホール船堀（東京都江戸川区）
  • Year and Date: 2014-10-14 – 2014-10-16
• [Presentation] Lewis Acid Catalyst for Recognition of Aromatic Compounds (2014)
  • Author(s): 安田 誠
  • Organizer: ETH Zurich-Osaka Univ. Joint Symposium
  • Place of Presentation: 大阪大学（大阪府豊中市）
  • Year and Date: 2014-10-09 – 2014-10-10
  • Invited
• [Presentation] Control of Selectivity for Aromatic Compounds by Cage-Shaped Metal Complexes with Modification of Their Ligands (2014)
  • Author(s): Hikaru Maruyama, Koichi Nakaoka, Makoto Yasuda, Akio Baba
  • Organizer: ETH Zurich-Osaka Univ. Joint Symposium
  • Place of Presentation: 大阪大学（大阪府豊中市）
  • Year and Date: 2014-10-09 – 2014-10-10
• [Presentation] GaBr3-Catalyzed Cross-Coupling Reaction between Enol Derivatives and Ketene Silyl Acetals via Carbogallation (2014)
  • Author(s): Yoshihiro Nishimoto, Yuji Kita, Makoto Yasuda, Akio Baba
  • Organizer: ETH Zurich-Osaka Univ. Joint Symposium
  • Place of Presentation: 大阪大学（大阪府豊中市）
  • Year and Date: 2014-10-09 – 2014-10-10
• [Presentation] Lewis Acid Catalyst for Recognition of Aromatic Compounds (2014)
  • Author(s): Makoto Yasuda
  • Organizer: ETH Zurich-Osaka Univ. Joint Symposium
  • Place of Presentation: Sigma-Hall, Toyonaka Campus, Osaka University, Japan
  • Year and Date: 2014-10-09
  • Int'l Joint Research / Invited
• [Presentation] 紫外線照射による有機スズ種とアルキルハライド類とのインジウムまたはガリウムハライド触媒ラジカル反応 (2014)
  • Author(s): 鈴木 至・江住直人・安田 誠・馬場章夫
  • Organizer: 第61回有機金属化学討論会
  • Place of Presentation: 九州大学（福岡県福岡市）
  • Year and Date: 2014-09-23 – 2014-09-25
• [Presentation] 臭化ガリウム触媒を用いるエノール誘導体とケテンシリルアセタールのカップリング反応の展開と機構解明 (2014)
  • Author(s): 西本能弘・喜多悠二・安田 誠・馬場章夫
  • Organizer: 第61回有機金属化学討論会
  • Place of Presentation: 九州大学（福岡県福岡市）
  • Year and Date: 2014-09-23 – 2014-09-25
• [Presentation] アンモニウム塩添加を鍵とする可視光酸化還元触媒によるアリルホウ素試薬を用いたαーハロカルボニル化合物のアリル化反応 (2014)
  • Author(s): 江住直人・鈴木 至・安田 誠・馬場章夫
  • Organizer: 第61回有機金属化学討論会
  • Place of Presentation: 九州大学（福岡県福岡市）
  • Year and Date: 2014-09-23 – 2014-09-25
• [Presentation] 配位子修飾によるかご型錯体の芳香族選択性制御 (2014)
  • Author(s): 丸山 輝・安永亮佑・西本能弘・安田 誠・馬場章夫
  • Organizer: 第25回基礎有機化学討論会
  • Place of Presentation: 東北大学（宮城県仙台市）
  • Year and Date: 2014-09-07 – 2014-09-09
• [Presentation] 複素環導入によるかご型ホウ素錯体のルイス酸性の精密制御 (2014)
  • Author(s): 安永 亮佑・西本 能弘・安田 誠・馬場章夫
  • Organizer: 第３４回有機合成若手セミナー 明日の有機合成を担う人のために
  • Place of Presentation: 大阪大学（大阪府豊中市）
  • Year and Date: 2014-08-05
• [Presentation] 可視光酸化還元触媒によるアリルホウ素試薬を用いたα-ハロカルボニル化合物のアリル化反応 (2014)
  • Author(s): 鈴木 至・江住 直人・安田 誠
  • Organizer: 第３４回有機合成若手セミナー 明日の有機合成を担う人のために
  • Place of Presentation: 大阪大学（大阪府豊中市）
  • Year and Date: 2014-08-05
• [Presentation] Effective Synthesis of Functionalized Propargyl Ethers with Acetals and Terminal Alkynes Catalyzed by Zn(II) Chloride (2014)
  • Author(s): 鈴木 至・安田 誠・馬場章夫
  • Organizer: The XXXVI International Conference on Organometallic Chemistry
  • Place of Presentation: ロイトン札幌（北海道札幌市）
  • Year and Date: 2014-07-13 – 2014-07-18
• [Presentation] Carbobismuthination of Carbon-Carbon Multiple Bonds by Using Bismuth Trihalides and Ketene Silyl Acetals (2014)
  • Author(s): 西本能弘・竹内 翠・安田 誠・馬場章夫
  • Organizer: The XXXVI International Conference on Organometallic Chemistry
  • Place of Presentation: ロイトン札幌（北海道札幌市）
  • Year and Date: 2014-07-13 – 2014-07-18
• [Presentation] Gallium Tribromide Accelerated Alkynylation of α-halo Carbonyl Compounds with Alkynylstannanes by UV Irradiation (2014)
  • Author(s): 鈴木 至・江住直人・安田 誠・馬場章夫
  • Organizer: The XXXVI International Conference on Organometallic Chemistry
  • Place of Presentation: ロイトン札幌（北海道札幌市）
  • Year and Date: 2014-07-13 – 2014-07-18
• [Presentation] 有機化学で金属性状を緻密に制御する －新しい選択性発現をめざして- (2014)
  • Author(s): 安田 誠
  • Organizer: セミナー“化学千一夜” 「あすの化学への夢を語ろう」
  • Place of Presentation: Ｉ＆Ｉ ＬＡＮＤ（大阪府四条畷市）
  • Year and Date: 2014-06-13 – 2014-06-14
  • Invited
• [Presentation] Structurally Designed Cage-Shaped Borate Esters for Selective Reactions as a Catalyst (2013)
  • Author(s): Makoto Yasuda
  • Organizer: 1st International Conference on “Recent Trends in Organometallic Compounds and their Industrial Applications” (OMCA-2013)
  • Place of Presentation: Kalinga Institute of Industrial Technology (KIIT University), Bhubaneswar, Odisha, India
  • Invited
• [Presentation] カゴ型ホウ素錯体の多様な修飾によるルイス酸性制御 (2012)
  • Author(s): 安田 誠
  • Organizer: 第５９回有機金属化学討論会
  • Place of Presentation: 大阪大学吹田キャンパス