Development of one-pot enantioselective construction of densely functionalized bicyclic compound using organocatalyst

• Project/Area Number: 26410121
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Synthetic chemistry
• Research Institution: Hiroshima University
• Principal Investigator: Takagi Ryukichi 広島大学, 理学研究科, 助教 (90304394)
• Project Period (FY): 2014-04-01 – 2017-03-31
• Project Status: Completed (Fiscal Year 2016)
• Budget Amount: ¥5,070,000 (Direct Cost: ¥3,900,000、Indirect Cost: ¥1,170,000); Fiscal Year 2016: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000); Fiscal Year 2015: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000); Fiscal Year 2014: ¥2,730,000 (Direct Cost: ¥2,100,000、Indirect Cost: ¥630,000)
• Keywords: 有機分子触媒 / Michael反応 / 不斉合成 / エナンチオ選択性 / 有機触媒

Outline of Final Research Achievements

In this research, one-pot asymmetric construction of densely functionalized bicyclic compound by successive Michael reactions of cyclohexanone derivatives and acrylate derivatives bearing a leaving group was investigated. The enantioselective intramolecular Michael reaction of cyclohexanone derivatives and acrylate derivatives, which is essential for the asymmetric construction, was achieved by using quaternary ammonium salt derived from cinchona alkaloid. On the basis of the enantioselective Michael reaction, one-pot asymmetric construction of densely functionalized bicyclic compounds was also achieved.

Research Products

• [Journal Article] Design and Synthesis of a 4-Nitrobromobenzene Derivative Bearing an Ethylene Glycol Tetraacetic Acid Unit for a New Generation of Caged Calcium Compounds with Two-Photon Absorption Properties in the Near-IR Region and Their Application in Vivo (2016)
  • Author(s): Satish Jakkampudi, Manabu Abe, Naomitsu Komori Ryukichi Takagi, Ko Furukawa, Claudine Katan, Wakako Sawada, Noriko Takahashi, and Haruo Kasai
  • Journal Title: ACS Omega Volume: 1 Issue: 2 Pages: 193-201
  • DOI: 10.1021/acsomega.6b00119
  • Peer Reviewed / Open Access / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Paterno-Buechi photochemical [2+2] cycloaddition of aromatic carbonyl compounds with 2-siloxy-1H-pyrrole derivatives (2016)
  • Author(s): Jianfei Xue, Manabu Abe, and Ryukichi Takagi
  • Journal Title: J. Phys. Org. Chem. Volume: 30 Issue: 4
  • DOI: 10.1002/poc.3632
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Organocatalytic asymmetric desymmetrization of 4,4-disubstituted cyclohexadienones via intermolecular Diels-Alder reaction. (2015)
  • Author(s): Ryukichi Takagi, Takehiko Nishi
  • Journal Title: Organic & Biomolecular Chemistry Volume: 13 Issue: 45 Pages: 11039-11045
  • DOI: 10.1039/c5ob01760b
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Formation of isomerized E,Z-configured 1,3-dienes in construction of macrocyclic trienes by diene-ene RCM (2015)
  • Author(s): R. Takagi, K. Tanaka, K. Yamamoto, Y. Hiraga, S. Kojima, M. Abe
  • Journal Title: Bulletin of the Chemical Society of Japan Volume: 88 Issue: 1 Pages: 146-148
  • DOI: 10.1246/bcsj.20140250
  • NAID: 130004690771
  • Peer Reviewed / Open Access
• [Presentation] キラルリン酸をテンプレートとしたエナンチオ選択的[2+2]環化付加反 応の検討 (2017)
  • Author(s): 田渕 千裕・高木 隆吉・安倍 学
  • Organizer: 日本化学会第９７春季年会
  • Place of Presentation: 横浜
  • Year and Date: 2017-03-16
• [Presentation] 新規ビススルホンイミドを用いた不斉ルイス酸触媒反応の検討 (2017)
  • Author(s): 山﨑 侑平・高木 隆吉・安倍 学
  • Organizer: 日本化学会第９７春季年会
  • Place of Presentation: 横浜
  • Year and Date: 2017-03-16
• [Presentation] Regio- and steteroselective photochemical-[2+2] cycloaddition reaction (Paterno-Buchi Reaction) of aromatic carbonyl compounds with pyrrole dericatives (2016)
  • Author(s): J. Xue, M. Abe, R. Takagi
  • Organizer: 2016年光化学討論会
  • Place of Presentation: 東京
  • Year and Date: 2016-09-06
• [Presentation] 新規ビススルホンイミドを用いた不斉ルイス酸触媒反応の検討 (2016)
  • Author(s): 山崎侑平・高木隆吉・安倍 学
  • Organizer: 第２７回基礎有機化学討論会
  • Place of Presentation: 広島
  • Year and Date: 2016-09-01
• [Presentation] 二光子吸収能を有するEGTA(Ethylene Glycol Tetraaceticacid)誘導体ケージドカルシウムの設計、合成と生体内における応用 (2016)
  • Author(s): Satish Jakkampudi・安倍 学・高木隆吉・河西春郎
  • Organizer: 第２７回基礎有機化学討論会
  • Place of Presentation: 広島
  • Year and Date: 2016-09-01
• [Presentation] 芳香族カルボニル化合物とピロール誘導体の光[2+2]付加環化反応（パターノ－ビュッヒ反応）における位置および立体選択性 (2016)
  • Author(s): Xue Jianfei・安倍 学・高木隆吉
  • Organizer: 第２７回基礎有機化学討論会
  • Place of Presentation: 広島
  • Year and Date: 2016-09-01
• [Presentation] REGIO- AND STEREOSELECTIVITY IN THE PHOTOCHEMICAL [2+2] CYCLOADDITION REACTION (PATERNO-BUCHI REACTION) OF AROMATIC CARBONYL COMPOUNDS WITH PYRROLE DERIVATIVES (2016)
  • Author(s): Jianfei Xue, Ryukichi Takagi, Manabu Abe
  • Organizer: 26th IUPAC International Symposium on Photochemistry
  • Place of Presentation: 大阪
  • Year and Date: 2016-04-03
  • Int'l Joint Research
• [Presentation] DESIGHN AND SYNTHESIS OF A ETHYLENE GLYCOL TETRAACETICACID (EGTA) DERIVATIVE FOR NEW GENERATION OF CAGED CALCIUM COMPOUNDS WITH TWOPHOTON ABSORPTION (TPA) PROPERTY, AND IT’S APPILICATIONS IN VIVO (2016)
  • Author(s): Satish Jakkampudi, Rukichi Takagi, Manabu Abe
  • Organizer: 26th IUPAC International Symposium on Photochemistry
  • Place of Presentation: 大阪
  • Int'l Joint Research
• [Presentation] Design and synthesis of new caged calcium with high two-photon absorption character (2015)
  • Author(s): Satish Jakkampudi, Manabu Abe, Ryukichi Takagi, Claudine Katan
  • Organizer: Pacifichem2015
  • Place of Presentation: ホノルル（米国）
  • Year and Date: 2015-12-15
• [Presentation] Organocatalytic asymmetric Michael reaction of cyclic β-ketoesters and Morita–Baylis–Hillman derivatives bearing a leaving group (2015)
  • Author(s): Ryukichi Takagi, Emi Fujii, Hirotoshi Kondo
  • Organizer: Pacifichem2015
  • Place of Presentation: ホノルル（米国）
  • Year and Date: 2015-12-15
• [Presentation] Synthesis of strong chiral Brønsted acids bearing an adjacent sulfonimide and its catalitic ability in hydroamination (2015)
  • Author(s): Toshiya Ichiki, Ryukichi Takagi , Manabu Abe
  • Organizer: Pacifichem2015
  • Place of Presentation: ホノルル（米国）
  • Year and Date: 2015-12-15
• [Presentation] Design and synthesis of new two-photon-absorption (TPA) chromophore with EGTA unit (2015)
  • Author(s): S. Jakkampudi, R. Takagi, C. Katan, M. Abe.
  • Organizer: 2014光化学討論会
  • Place of Presentation: 大阪
  • Year and Date: 2015-09-09
• [Presentation] キラルリン酸触媒によるジエノンの不斉非対称化Diels-Alder 反応 (2015)
  • Author(s): 高木隆吉・西 長彦
  • Organizer: 日本化学会第９５春季年会
  • Place of Presentation: 船橋、日本大学船橋キャンパス
  • Year and Date: 2015-03-26 – 2015-03-29
• [Presentation] 光励起ケトンによるラジカル付加反応における脱離基の調査 (2015)
  • Author(s): 田村孝明・高木隆吉・安倍 学
  • Organizer: 日本化学会第９５春季年会
  • Place of Presentation: 船橋、日本大学船橋キャンパス
  • Year and Date: 2015-03-26 – 2015-03-29
• [Presentation] スルホンイミド基が隣接したキラルブレンステッド酸の酸性度とその反応性 (2015)
  • Author(s): 市来隼哉・高木隆吉・安倍 学
  • Organizer: 日本化学会第９５春季年会
  • Place of Presentation: 船橋、日本大学船橋キャンパス
  • Year and Date: 2015-03-26 – 2015-03-29
• [Presentation] ケト基を有するビナフチル誘導体によるエナンチオ選択的な光励起C-H官能基化反応の開発 (2014)
  • Author(s): 田村孝明, 高木隆吉, 安倍 学
  • Organizer: 2014光化学討論会
  • Place of Presentation: 札幌、北海道大学
  • Year and Date: 2014-10-11 – 2014-10-13
• [Presentation] ビナフチル誘導体を用いた光励起C-H 官能基化反応の検討 (2014)
  • Author(s): 田村孝明, 高木隆吉, 安倍 学
  • Organizer: 第3回 JACI/GSCシンポジウム
  • Place of Presentation: 東京、東京国際フォーラム
  • Year and Date: 2014-05-22 – 2014-05-23