Cooperative Effect of Multi-Active Sites in Catalytic Reactions

• Project/Area Number: 25288019
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Partial Multi-year Fund
• Section: 一般
• Research Field: Organic chemistry
• Research Institution: Tokyo University of Science (2015); Kanazawa University
• Principal Investigator: Endo Kohei 東京理科大学, 理学部, 准教授 (70454064)
• Project Period (FY): 2013-04-01 – 2016-03-31
• Project Status: Completed (Fiscal Year 2015)
• Budget Amount: ¥18,330,000 (Direct Cost: ¥14,100,000、Indirect Cost: ¥4,230,000); Fiscal Year 2015: ¥7,410,000 (Direct Cost: ¥5,700,000、Indirect Cost: ¥1,710,000); Fiscal Year 2014: ¥7,410,000 (Direct Cost: ¥5,700,000、Indirect Cost: ¥1,710,000); Fiscal Year 2013: ¥3,510,000 (Direct Cost: ¥2,700,000、Indirect Cost: ¥810,000)
• Keywords: 分子触媒 / 有機金属化学 / クラスター / 有機化学 / 多核金属錯体触媒 / 金属クラスター触媒 / 超分子化学 / 触媒反応 / 立体選択的 / 有機金属錯体 / 元素戦略

Outline of Final Research Achievements

The present project for the development of multi-active sites in catalysis revealed the electrophilic activation by neighboring atoms for the activation of a reactive site. (1) The use of Fischer-type carbene complexes as electrophilic organometallic intermediates realized the tandem nucleophilic addition reaction. The use of stable cyclopropenes as carbene precursors provides a allylmetal intermediates via the reaction with organometallic reagents, followed by the tandem allylation reaction of appropriate electrophiles took place efficiently. (2) The multi-metallic catalysts achieved the asymmetric conjugate addition to give chiral furnaces bearing a quaternary stereogenic center. (3) The bimetallic cluster system showed unique chemo- and stereoselectivity in the reduction of alkynes using formic acid.

Research Products

• [Journal Article] Silver-Catalyzed Allylation of Ketones and Intramolecular Cyclization via Carbene Intermediates from Cyclopropenes Under Ambient Conditions (2016)
  • Author(s): Takeo Nakano, Kohei Endo, Yutaka Ukaji
  • Journal Title: Chemistry An Asian Journal Volume: 11 Issue: 5 Pages: 713-721
  • DOI: 10.1002/asia.201501196
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Copper(I)-Catalyzed Carbometalation of Nonfunctionalized Cyclopropenes Using Organozinc and Grignard Reagents (2015)
  • Author(s): Takeo Nakano, Kohei Endo, Yutaka Ukaji
  • Journal Title: Synlett Volume: 26 Issue: 05 Pages: 671-675
  • DOI: 10.1055/s-0034-1379959
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Catalytic Tandem C-C Bond Formation/Cleavage of Cyclopropene for Allylzincation of Aldehydes or Aldimine Using Organozinc Reagents. (2014)
  • Author(s): T. Nakano, K. Endo, Y. Ukaji
  • Journal Title: Org. Lett. Volume: 16 Issue: 5 Pages: 1418-1421
  • DOI: 10.1021/ol500208r
  • Peer Reviewed
• [Journal Article] Highly Chemo-, Enantio-, and Regioselective Synthesis of α,α-Disubstituted Furanones via Cu-Catalyzed Conjugate Addition (2014)
  • Author(s): Kohei Endo, Sayuri Yakeishi, Ryotaro Takayama, Takanori Shibata
  • Journal Title: Chemistry European Journal Volume: 20 Issue: 29 Pages: 8893-8897
  • DOI: 10.1002/chem.201403446
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] One-Pot Cross-Coupling of Diborylmethane for the Synthesis of Dithienylmethane Derivatives (2014)
  • Author(s): Kohei Endo, Takafumi Ishioka, Takanori Shibata
  • Journal Title: Synlett Volume: 25 Issue: 15 Pages: 2184-2188
  • DOI: 10.1055/s-0034-1378561
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Chemoselective Carbozincation of Cyclopropene for C–C Bond Formation and Cleavage Sequence in Single Operation (2013)
  • Author(s): K. Endo, T. Nakano, S. Fujinami, Y. Ukaji
  • Journal Title: Eur. J. Org. Chem. Volume: 2013 Issue: 29 Pages: 6514-6518
  • DOI: 10.1002/ejoc.201301026
  • Peer Reviewed
• [Journal Article] Silver(I) Oxide-Promoted Cross-Coupling Reaction of (Diborylmethyl)trimethylsilane (2013)
  • Author(s): Kohei Endo, Fumiya Kurosawa, Yutaka Ukaji
  • Journal Title: Chem. Lett. Volume: 42 Issue: 11 Pages: 1363-1365
  • DOI: 10.1246/cl.130643
  • NAID: 130004426834
  • Peer Reviewed
• [Presentation] 有機アルミニウム試薬を用いるシクロプロペンの[2+2]環化付加反応の開発 (2016)
  • Author(s): 関谷卓也、遠藤恆平、宇梶裕
  • Organizer: 日本化学会第９６春季年会
  • Place of Presentation: 京都府、京田辺市
  • Year and Date: 2016-03-24
• [Presentation] 複核銅錯体触媒を用いた共役ジエノンへの有機金属試薬の不斉 共役付加反応の開発 (2015)
  • Author(s): 小林友毅，遠藤恆平，宇梶裕
  • Organizer: 日本化学会第９５春季年会
  • Place of Presentation: 日本大学理工学部船橋キャンパス
  • Year and Date: 2015-03-28
  • Invited
• [Presentation] 隣接原子による求電子的活性化を鍵とする有機金属触媒反応の開発 (2015)
  • Author(s): 遠藤恆平
  • Organizer: 日本化学会第９５春季年会
  • Place of Presentation: 日本大学理工学部船橋キャンパス
  • Year and Date: 2015-03-27
  • Invited
• [Presentation] 銀触媒によるシクロプロペンからのビニルカルベノイド中間体 の発生と連続するアリル化反応の開発 (2015)
  • Author(s): 中野健央，遠藤恆平，宇梶裕
  • Organizer: 日本化学会第９５春季年会
  • Place of Presentation: 日本大学理工学部船橋キャンパス
  • Year and Date: 2015-03-27
  • Invited
• [Presentation] 軌道相互作用を指向した有機金属中間体の制御 (2014)
  • Author(s): 遠藤恆平
  • Organizer: 有機金属若手の会 夏の学校
  • Place of Presentation: 休暇村 大久野島
  • Year and Date: 2014-09-01 – 2014-09-03
  • Invited
• [Presentation] ジボリルメタンをC1源とする臭化へテロアリールとの連続的鈴木宮浦クロスカップリング反応 (2014)
  • Author(s): 石岡孝文、遠藤恆平、柴田高範
  • Organizer: 日本化学会第９４春季年会
  • Place of Presentation: 愛知県（名古屋）、名古屋大学
  • Invited
• [Presentation] 有機亜鉛試薬を用いたシクロプロペンの開環反応と連続的分子間アリル化反応の開発 (2014)
  • Author(s): 中野健央、遠藤恆平、宇梶裕
  • Organizer: 日本化学会第９４春季年会
  • Place of Presentation: 愛知県（名古屋）、名古屋大学
  • Invited
• [Presentation] 複核金属錯体を用いる不斉共役付加反応によるメチル／トリフルオロメチル置換４級不斉炭素の構築 (2014)
  • Author(s): 高山遼太郎、遠藤恆平、柴田高範
  • Organizer: 日本化学会第９４春季年会
  • Place of Presentation: 愛知県（名古屋）、名古屋大学
  • Invited
• [Presentation] Development of Intricate Organometallic Intermediates (2013)
  • Author(s): Kohei Endo
  • Organizer: International Symposium on Catalysis and Fine Chemicals 2013
  • Place of Presentation: 中国（北京）、人民大学
  • Invited
• [Presentation] 有機亜鉛試薬を用いるシクロプロパン環の化学選択的開環反応を伴った新奇タンデム反応の開発 (2013)
  • Author(s): 中野健央、遠藤恆平、宇梶裕
  • Organizer: 有機合成化学協会北陸セミナー
  • Place of Presentation: 石川県（金沢）、石川県青少年総合研修センター
  • Invited
• [Remarks] ENDO Research Group
  • URL: http://endorg.secret.jp/wp/
• [Remarks] 遠藤研究室
  • URL: http://endorg.secret.jp/lab/
• [Remarks] ENDO Research Group
  • URL: http://endorg.secret.jp/wp/