Natural Product Synthesis by Utilizing Compact and Multifunctional Properties of Cyano Group

• Project/Area Number: 24350018
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Partial Multi-year Fund
• Section: 一般
• Research Field: Organic chemistry
• Research Institution: Hokkaido University
• Principal Investigator: TANINO Keiji 北海道大学, 理学研究院, 教授 (40217146)
• Project Period (FY): 2012-04-01 – 2015-03-31
• Project Status: Completed (Fiscal Year 2014)
• Budget Amount: ¥18,070,000 (Direct Cost: ¥13,900,000、Indirect Cost: ¥4,170,000); Fiscal Year 2014: ¥5,850,000 (Direct Cost: ¥4,500,000、Indirect Cost: ¥1,350,000); Fiscal Year 2013: ¥5,720,000 (Direct Cost: ¥4,400,000、Indirect Cost: ¥1,320,000); Fiscal Year 2012: ¥6,500,000 (Direct Cost: ¥5,000,000、Indirect Cost: ¥1,500,000)
• Keywords: 有機化学 / 天然物化学 / 全合成 / ニトリル

Outline of Final Research Achievements

The synthetic studies on Tubiferal A, Azadirachtin, and Phorbol were carried out on the basis of new reactions utilizing alkanenitriles. The unique properties of a cyano group, which is sterically compact and linear in shape, were found to be advantageous for forming carbocyclic compounds possessing hindered carbon-carbon bonds. For example, construction of the 5-7 bicyclic skeleton of Phorbol was achieved by the divinylcyclopropane rearrangement reaction of a cyanocyclopropane derivative.

Research Products

• [Journal Article] Synthetic Studies on Azadirachtin: Construction of the ABC Ring System via the Diels-Alder Reaction of a Vinyl Allenylsilane Derivative (2015)
  • Author(s): Kentaro Sakurai and Keiji Tanino
  • Journal Title: Tetrahedron Letters Volume: 56 Issue: 3 Pages: 496-499
  • DOI: 10.1016/j.tetlet.2014.12.062
  • Peer Reviewed
• [Journal Article] Synthetic studies on taxanes : construction of the tricyclic skeleton on the basis of the [6+2] cycloaddition reaction (2014)
  • Author(s): 花田良輔, 三田地克彦, 谷野圭持
  • Journal Title: Tetrahedron Letters Volume: 55 Issue: 5 Pages: 1097-1099
  • DOI: 10.1016/j.tetlet.2013.12.096
  • Peer Reviewed
• [Journal Article] Stereoselective Synthesis of the Right-hand Segment of Tubiferal A (2014)
  • Author(s): Takahiro Hiramatsu, Motomasa Takahashi, Keiji Tanino
  • Journal Title: Tetrahedron Letters Volume: 55 Issue: 6 Pages: 1145-1147
  • DOI: 10.1016/j.tetlet.2013.12.069
  • Peer Reviewed
• [Journal Article] Synthesis of 1-Acetyl-2-silyoxycycloheptane Derivatives via Highly Stereoselective formal [5+2] Cycloaddition Reaction (2014)
  • Author(s): Mami Kudo, Fumikatsu Kondo, Hideki Maekawa, Tadashi Shimizu, Masaaki Miyashita, Keiji Tanino
  • Journal Title: Tetrahedron Letters Volume: 55 Issue: 6 Pages: 1192-1195
  • DOI: 10.1016/j.tetlet.2013.12.102
  • Peer Reviewed
• [Journal Article] Cyanoazulene-based Multi-stage Redox Systems Prepared from Vinylcyclopropane-carbonitrile and Cyclopentenone via Divinylcyclopropane-rearrangement Approach (2014)
  • Author(s): Keiji Tanino, Takumasa Yamada, Fumihiko Yoshimura, and Takanori Suzuki
  • Journal Title: Chemistry Letters Volume: 43 Issue: 5 Pages: 607-609
  • DOI: 10.1246/cl.131149
  • NAID: 130004868100
  • Peer Reviewed
• [Journal Article] N-Acyl-N-tosylhydrazine as a Synthon To Construct Tetrasubstituted Carbon Centers Possessing a Nitrogen Group (2014)
  • Author(s): Namba, K.; Shobo, Y.; Fujimoto, K.; Shoji, I.; Yoshida, M.; Tanino, K.
  • Journal Title: Eur. J. Org. Chem. Volume: 2014 Issue: 24 Pages: 5196-5203
  • DOI: 10.1002/ejoc.201402650
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Nucleophilic Addition Reactions of Nitriles to Nitrones under Mild Silylation Conditions (2014)
  • Author(s): Fumihiko Yoshimura, Taiki Abe, and Keiji Tanino
  • Journal Title: Synlett Volume: 25 Issue: 13 Pages: 1863-1868
  • DOI: 10.1055/s-0034-1378274
  • NAID: 120005647261
  • Peer Reviewed / Open Access
• [Journal Article] Inhibition of C-terminal truncated PPM1D enhances the effect of doxorubicin on cell viability in human colorectal carcinoma cell line. (2014)
  • Author(s): Yuuki Kozakai, Rui Kamada, Yuhei Kiyota, Fumihiko Yoshimura, Keiji Tanino, Kazuyasu Sakaguchi
  • Journal Title: Bioorganic & Medicinal Chemistry Letters Volume: 24 Issue: 24 Pages: 5593-5596
  • DOI: 10.1016/j.bmcl.2014.10.093
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Synthesis of 2-Cyano-1,4-cycloheptadiene Derivatives via Divinylcyclopropane Rearrangement and Alkylation of Novel Cycloheptadienyl Anion Species (2013)
  • Author(s): Takumasa Yamada, Fumihiko Yoshimura, Keiji Tanino
  • Journal Title: Tetrahedron Letters Volume: 54 Issue: 6 Pages: 522-525
  • DOI: 10.1016/j.tetlet.2012.11.070
  • Peer Reviewed
• [Journal Article] Transformations of 1-(Oxiranylmethyl)-1,2,3-triazoles into 2-(Oxiranylmethyl)-1,2,3-triazoles and Alkanenitriles (2013)
  • Author(s): Kosuke Namba, Ayumi Osawa, Akane Mera, Keiji Tanino
  • Journal Title: Synlett Volume: 24 Issue: 02 Pages: 207-210
  • DOI: 10.1055/s-0032-1317937
  • NAID: 120005358931
  • Peer Reviewed
• [Journal Article] Synthesis of Tetrasubstituted Pyrrolidine Derivatives Employing β-Lactam as a Chiral Building Block (2013)
  • Author(s): Genta Tadano, Koji Ishikura, Keiji Tanino
  • Journal Title: Heterocycles Volume: 87 Issue: 11 Pages: 2267-2281
  • DOI: 10.3987/com-13-12812
  • NAID: 40019844682
  • Peer Reviewed
• [Journal Article] A small molecule inhibitor of p53-inducible protein phosphatase PPM1D (2012)
  • Author(s): 八木寛陽
  • Journal Title: Bioorganic & Medicinal Chemistry Letters Volume: VOL.22 Issue: 1 Pages: 729-732
  • DOI: 10.1016/j.bmcl.2011.10.084
  • Peer Reviewed
• [Journal Article] Intramolecular Conjugate Addition ofα,β-Unsaturated Lactones Having an Alkanenitrile Side Chain : Stereocontrolled Construction of Carbocycles with Quaternary Carbon Atoms (2012)
  • Author(s): Yoshimura, F.; Torizuka, M.; Mori, G.; Tanino, K.
  • Journal Title: Synlett Volume: 23巻 Issue: 02 Pages: 251-254
  • DOI: 10.1055/s-0031-1290074
  • Peer Reviewed
• [Journal Article] Hg(OTf)2-Catalyzed Vinylogous Semi-Pinacol Rearrangement Leading to 1,4-Dihydroquinolines (2012)
  • Author(s): 谷野圭持、難波康祐, ほか3名
  • Journal Title: Organic Letters Volume: 14 Pages: 1222-1225
  • Peer Reviewed
• [Journal Article] Stereocontrolled synthesis of Carbocyclic Compounds with a Quaternary Carbon Atom based on SN2' Alkylation of γ,δ-Epoxy-α,β-unsaturated Ketones (2012)
  • Author(s): 谷野圭持、吉村文彦, ほか1名
  • Journal Title: Organic & Biomolecular Chemistry Volume: 10 Issue: 28 Pages: 5431-5442
  • DOI: 10.1039/c2ob25719j
  • NAID: 120005228736
  • Peer Reviewed
• [Journal Article] A Concese [4+3]Cycloadditions of Pyrroles Leading to Tropinone Derivatives (2012)
  • Author(s): Fuchigami, R. ; Namba, K. ; Tanino, K.
  • Journal Title: Tetrahedron Letter Volume: 53 Issue: 43 Pages: 5725-5728
  • DOI: 10.1016/j.tetlet.2012.07.130
  • Peer Reviewed
• [Journal Article] One-Pot Synthesis of Highly Fluorescent 2,5-Disubstituted-1,3a,6a-triazapentalene (2012)
  • Author(s): K. Namba, A. Mera, A. Osawa, E. Sakuda, N. Kitamura and K. Tanino
  • Journal Title: Org. Lett. Volume: 14 Issue: 21 Pages: 5554-5557
  • DOI: 10.1021/ol302668y
  • Peer Reviewed
• [Presentation] 新しい縮環骨格構築法を基盤とする高次構造天然物の全合成 (2013)
  • Author(s): 谷野圭持
  • Organizer: 日本化学会第93春季年会(
  • Place of Presentation: 立命館大学(草津市)(招待講演)
  • Year and Date: 2013-03-23
• [Presentation] 社会に役立つ有機合成を求めて : シストセンチュウふ化促進物質の全合成 (2013)
  • Author(s): 谷野圭持
  • Organizer: 平成24年度関学化字フォーラム「有機合成化学を究める」
  • Place of Presentation: 関西学院大学(三田)(招待講演)
  • Year and Date: 2013-01-28
• [Presentation] 社会に役立つ「ものづくり」としての多段階合成を求めて : シストセンチュウふ化促進物質の全合成 (2012)
  • Author(s): 谷野圭持
  • Organizer: 有機合成化学を起点とするものづくり戦略 第2回ミニシンポジウム
  • Place of Presentation: 北海道大学(札幌市)(招待講演)
  • Year and Date: 2012-09-28
• [Presentation] 新しい高次付加環化反応を基盤とする天然物合成
  • Author(s): 谷野 圭持
  • Organizer: 理研セミナー「未来に繋ぐ天然物合成化学」
  • Place of Presentation: 大阪大学（豊中市）
  • Invited
• [Presentation] シストセンチュウ孵化促進物質の不斉全合成
  • Author(s): 谷野 圭持
  • Organizer: 新学術領域研究「生合成マシナリー：生物活性物質構造多様性創出システムの解明と制御」第５回公開シンポジウム
  • Place of Presentation: 北海道大学（札幌市）
  • Invited