Research on CO2 incorporation reactions for synthetic organic chemistry

• Project/Area Number: 23350047
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Synthetic chemistry
• Research Institution: Keio University
• Principal Investigator: YAMADA Tohru 慶應義塾大学, 理工学部, 教授 (40296752)
• Project Period (FY): 2011-04-01 – 2015-03-31
• Project Status: Completed (Fiscal Year 2014)
• Budget Amount: ¥19,240,000 (Direct Cost: ¥14,800,000、Indirect Cost: ¥4,440,000); Fiscal Year 2013: ¥3,770,000 (Direct Cost: ¥2,900,000、Indirect Cost: ¥870,000); Fiscal Year 2012: ¥6,500,000 (Direct Cost: ¥5,000,000、Indirect Cost: ¥1,500,000); Fiscal Year 2011: ¥8,970,000 (Direct Cost: ¥6,900,000、Indirect Cost: ¥2,070,000)
• Keywords: 合成化学 / 触媒・化学プロセス / 二酸化炭素 / 廃棄物再資源化

Outline of Final Research Achievements

A silver/DBU catalyst system was developed for the effective synthesis of cyclic carbonate from the reaction of CO2 with propargylic alcohols in high yields under mild conditions. We found that the catalytic amount of silver benzoate with MTBD was effective catalytic system and the corresponding lactone derivatives were obtained in high yields. It was found that a silver catalyst successfully promoted the incorporation of CO2 into o-alkynylanilines to afford the corresponding benzoxazine-2-ones bearing Z exo-olefin at the activated C-C triple bond. In the presence of a catalytic amount of silver salt, various o-alkynylanilines were treated with carbon dioxide and DBU under mild reaction conditions to afford the corresponding 4-hydroxyquinolin-2(1H)-one derivatives in high yield. The key step is proposed as the generation of the isocyanate and the enolate through C-O bond cleavage and new C-C bond formation induced by deprotonation after formation of the benzoxazin-2-one.

Research Products

• [Journal Article] Cobalt-Catalyzed Reductive Carboxylation of α,β-Unsaturated Compounds with Carbon Dioxide (2015)
  • Author(s): C. Hayashi, T. Hayashi, and T. Yamada
  • Journal Title: Bulletin of the Chemical Society of Japan Volume: 88 Issue: 6 Pages: 862-870
  • DOI: 10.1246/bcsj.20150043
  • NAID: 130005075685
  • ISSN: 0009-2673, 1348-0634
  • Peer Reviewed
• [Journal Article] Carbon Dioxide Incorporation into Alkylenic Compounds Mediated by Silver Catalyst (2014)
  • Author(s): S. Kikuchi and T. Yamada
  • Journal Title: The Chemical Record Volume: 14 Issue: 1 Pages: 62-69
  • DOI: 10.1002/tcr.201300025
  • Peer Reviewed
• [Journal Article] Cobalt-Catalyzed Reductive Carboxylation on α,β-Unsaturated Nitriles with Carbon Dioxide (2014)
  • Author(s): C. Hayashi, T. Hayashi, S. Kikuchi and T. Yamada
  • Journal Title: Chemistry Letters Volume: 43 Issue: 4 Pages: 565-567
  • DOI: 10.1246/cl.131163
  • NAID: 130004868031
  • Peer Reviewed
• [Journal Article] Silver-catalyzed Efficient Synthesis of Vinylene Carbonate Derivatives from Carbon Dioxide (2014)
  • Author(s): R. Ugajin, S. Kikuchi, and T. Yamada
  • Journal Title: Synlett Volume: 25 Issue: 08 Pages: 1178-1180
  • DOI: 10.1055/s-0033-1341047
  • Peer Reviewed
• [Journal Article] Novel Method of Tetramic Acid Synthesis: Silver-Catalyzed Carbon Dioxide Incorporation into Propargylic Amine and Intramolecular Rearrangement (2014)
  • Author(s): T. Ishida, R. Kobayashi, and T. Yamada
  • Journal Title: Organic Letters Volume: 16 Issue: 9 Pages: 2430-2433
  • DOI: 10.1021/ol500806u
  • Peer Reviewed
• [Journal Article] Efficient Preparation of 4-Hydroxyquinolin-2(1H)-one Derivatives with Silver-Catalyzed Carbon Dioxide Incorporation and Intramolecular Rearrangement (2013)
  • Author(s): T. Ishida, S. Kikuchi, and T. Yamada
  • Journal Title: Organic Letters Volume: 15 Issue: 14 Pages: 3710-3713
  • DOI: 10.1021/ol401571r
  • Peer Reviewed
• [Journal Article] Silver-Catalyzed C-C Bond Formation with Carbon Dioxide: Significant Synthesis of Dihydroisobenzofurans (2013)
  • Author(s): K. Sekine, A. Takayanagi, S. Kikuchi, and T. Yamada
  • Journal Title: Chemical Communications Volume: 49 Issue: 96 Pages: 11320-11322
  • DOI: 10.1039/c3cc47221c
  • Peer Reviewed
• [Journal Article] Silver-Catalyzed Incorporation of Carbon Dioxide into o-Alkynylaniline Derivatives (2013)
  • Author(s): Tomonobu Ishida
  • Journal Title: Org. Lett. Volume: 15 Issue: 4 Pages: 848-851
  • DOI: 10.1021/ol303534w
  • Peer Reviewed
• [Journal Article] Catalytic C-C Bond Formation with Carbon Dioxide by Silver Catalyst (2012)
  • Author(s): Satoshi Kikuchi
  • Journal Title: Angew. Chem. Int. Ed. Volume: 51 Issue: 28 Pages: 6989-6992
  • DOI: 10.1002/anie.201201399
  • Peer Reviewed
• [Journal Article] Silver-Catalyzed Carbon Dioxide Incorporation and Rearrangement on Propargylic Derivatives (2011)
  • Author(s): S.Kikuchi, et al
  • Journal Title: Bulletin of the Chemical Society of Japan Volume: 84 Issue: 7 Pages: 698-717
  • DOI: 10.1246/bcsj.20110078
  • NAID: 130004152943
  • ISSN: 0009-2673, 1348-0634
  • Peer Reviewed
• [Journal Article] VCDを用いる光学活性環状炭酸エステルの絶対立体配置の決定 (2011)
  • Author(s): 山田徹
  • Journal Title: JASCO Report Volume: 53 Pages: 1-5
  • NAID: 40018864784
• [Presentation] Silver-Catalyzed C-C Bond Formation with Carbon Dioxide (2014)
  • Author(s): Tohru Yamada, Kohei Sekine, Tomonobu Ishida
  • Organizer: International Conference on Ormanometallic Chemistry 2014
  • Place of Presentation: ロイトン札幌 （北海道札幌市中央区）
  • Year and Date: 2014-07-13 – 2014-07-18
• [Presentation] 銀塩の触媒的アルキン活性化および分子内転位によるアルキニルアミン誘導体への二酸化炭素固定化反応（１） (2014)
  • Author(s): 石田智信・菊地哲・山田徹
  • Organizer: 日本化学会第94春季年会
  • Place of Presentation: 名古屋大学東山キャンパス （愛知県名古屋市千種区）
  • Year and Date: 2014-03-27 – 2014-03-30
• [Presentation] 銀塩の触媒的アルキン活性化および分子内転位によるアルキニルアミン誘導体への二酸化炭素固定化反応（２） (2014)
  • Author(s): 石田智信・小林遼・菊地哲・山田徹
  • Organizer: 日本化学会第94春季年会
  • Place of Presentation: 名古屋大学東山キャンパス （愛知県名古屋市千種区）
  • Year and Date: 2014-03-27 – 2014-03-30
• [Presentation] 銀触媒によるアルキンの活性化を利用するケトン化合物に対する炭素-炭素結合形成を伴う二酸化炭素固定化反応 (2014)
  • Author(s): 関根康平・石田智信・高柳綾乃・菊地哲・山田徹
  • Organizer: 日本化学会第94春季年会
  • Place of Presentation: 名古屋大学東山キャンパス （愛知県名古屋市千種区）
  • Year and Date: 2014-03-27 – 2014-03-30
• [Presentation] 二酸化炭素を用いるα,β-不飽和ニトリルのコバルト(II)触媒 還元的カルボキシル化反応 (2014)
  • Author(s): 林知佳・林卓夫・菊地哲・山田徹
  • Organizer: 日本化学会第94春季年会
  • Place of Presentation: 名古屋大学東山キャンパス （愛知県名古屋市千種区）
  • Year and Date: 2014-03-27 – 2014-03-30
• [Presentation] 銀触媒によるアルキンの活性化を鍵工程とする二酸化炭素固定化反応:炭素-炭素結合形成反応(1) (2012)
  • Author(s): 石田智信
  • Organizer: 第92日本化学会春季年会
  • Place of Presentation: 横浜市港北区
  • Year and Date: 2012-03-28
• [Presentation] 銀触媒によるアルキンの活性化を鍵工程とする二酸化炭素固定化反応:炭素-炭素結合形成反応(2) (2012)
  • Author(s): 関根康平
  • Organizer: 第92日本化学会春季年会
  • Place of Presentation: 横浜市港北区
  • Year and Date: 2012-03-28
• [Presentation] 触媒的不斉合成反応2題(1)コバルト錯体触媒による不斉ボロヒドリド還元反応の新展開(2)銀触媒による二酸化炭素の不斉固定化反応 (2012)
  • Author(s): 山田徹
  • Organizer: 触媒学会横浜地区講演会
  • Place of Presentation: 横浜市緑区(招待講演)
  • Year and Date: 2012-01-24
• [Presentation] Silver-Catalyzed Enantioselective CO_2 Incorporation into Bispropargylic Alcohols (2011)
  • Author(s): Tohru Yamada
  • Organizer: Catalysis and Fine Chemicals 2011
  • Place of Presentation: 奈良県奈良市(招待講演)
  • Year and Date: 2011-12-06
• [Presentation] Silver-Catalyzed Enantioselective CO_2 Incorporation into Bispropargylic Alcohols (2011)
  • Author(s): Tohru Yamada
  • Organizer: 10^<th> International Symposium on Organic Reactions (ISOR10)
  • Place of Presentation: 横浜市港北区(招待講演)
  • Year and Date: 2011-11-22
• [Presentation] 銀触媒による二酸化炭素の不斉固定化反応 (2011)
  • Author(s): 山田徹
  • Organizer: 第108回触媒討論会
  • Place of Presentation: 北海道北見市
  • Year and Date: 2011-09-20
• [Presentation] Silver-Catalyzed Enantioselective CO_2 Incorporation into Bispropargylic Alcohols (2011)
  • Author(s): Tohru Yamada
  • Organizer: 14^<th> Asian Chemical Congress 2011
  • Place of Presentation: Bangkok,タイ王国(招待講演)
  • Year and Date: 2011-09-08
• [Presentation] Silver-Catalyzed Enantioselective CO_2 Incorporation into Bispropargylic Alcohols (2011)
  • Author(s): Tohru Yamada
  • Organizer: Pre-Symposium at Siem Reap, 14^<th> Asian Chemical Congress 2011
  • Place of Presentation: Siem Reap,カンボジア(招待講演)
  • Year and Date: 2011-09-04
• [Presentation] Silver-Catalyzed Enantioselective Carbon Dioxide Incorporation into Bispropargylic Alcohols (2011)
  • Author(s): Tohru Yamada
  • Organizer: OMCOS16
  • Place of Presentation: 上海,中華人民共和国
  • Year and Date: 2011-07-25
• [Presentation] コバルト錯体触媒を用いるα,β-不飽和ニトリルの二酸化炭素による還元的カルボキシル化反応（１）
  • Author(s): 林 知佳
  • 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
• [Presentation] コバルト錯体触媒を用いるα,β-不飽和ニトリルの二酸化炭素による還元的カルボキシル化反応（２）
  • Author(s): 林 卓央
  • 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
• [Presentation] 銀触媒による炭素-炭素三重結合の活性化を鍵工程とする第２級プロパルギルアルコールへの二酸化炭素固定化反応
  • Author(s): 宇賀神 理恵
  • 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
• [Presentation] 銀触媒による炭素-炭素三重結合の活性化を鍵工程とするo-アルキニルアニリン誘導体への二酸化炭素固定化反応
  • Author(s): 石田 智信
  • 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
• [Presentation] 銀触媒によるアルキンの活性化を鍵工程とする二酸化炭素との炭素-炭素結合形成反応（１）
  • Author(s): 関根 康平
  • 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
• [Presentation] 銀触媒によるアルキンの活性化を鍵工程とする二酸化炭素との炭素-炭素結合形成反応（２）
  • Author(s): 髙栁 綾乃
  • 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
• [Presentation] Silver-Catalyzed Carbon Dioxide Incorporation Reaction on Alkyne Derivatives
  • Author(s): 山田 徹
  • Organizer: XXV International Conference on Organometallic Chemistry (ICOMC)
  • Place of Presentation: Lisbon, Portugal
• [Book] 二酸化炭素の直接利用最新技術 (2013)
  • Author(s): 菊地 哲
  • Total Pages: 7
  • Publisher: 株式会社エヌ・ティー・エス