Development of Reactions Based on New Utilization of Highly Reactive Species

• Project/Area Number: 16K08159
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Chemical pharmacy
• Research Institution: Kanazawa University
• Principal Investigator: Taniguchi Tsuyoshi 金沢大学, 薬学系, 助教 (60444204)
• Project Period (FY): 2016-04-01 – 2019-03-31
• Project Status: Completed (Fiscal Year 2018)
• Budget Amount: ¥4,810,000 (Direct Cost: ¥3,700,000、Indirect Cost: ¥1,110,000); Fiscal Year 2018: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000); Fiscal Year 2017: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000); Fiscal Year 2016: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
• Keywords: ボラン / ラジカル / アルキン / 環化反応 / ホウ素化反応 / ラクトン化反応 / ヒドロホウ素化 / ベンザイン / 有機化学 / 典型元素化学 / ホウ素化学

Outline of Final Research Achievements

We found 1,4-hydroboration of p-benzyne species with stable borane complexes. In the course of this study, we discovered three new reactions: (1) radical cyclization induced by addition of boryl radicals to alkynes, (2) radical trans-hydroboration of alkynes, (3) lactonization of propargyl acetates using boryl radicals.

Academic Significance and Societal Importance of the Research Achievements

ホウ素中心ラジカルは他のラジカル種に比べて合成化学での応用が非常に限られている。今回、研究代表者はホウ素中心ラジカルの多重結合への付加反応を見出し、有機化合物にホウ素を導入する新しい手法を開発することができた。有機ホウ素化合物は特異な物性を示すことから幅広い分野で興味を持たれている化合物であり、今回の知見は今後新しい医薬品や材料の開発につながるものと期待される。

Research Products

• [Int'l Joint Research] University of Pittsburgh(米国)
• [Int'l Joint Research] University of Pittsburgh(米国)
• [Int'l Joint Research] University of Ljubljana(スロベニア)
• [Int'l Joint Research] University of Pittsburgh(米国)
• [Int'l Joint Research] University of Ljubljana(スロベニア)
• [Journal Article] Esters as Radical Acceptors: β-NHC-Borylalkenyl Radicals Induce Lactonization by C-C Bond Formation/Cleavage on Esters (2019)
  • Author(s): Shimoi Masaki、Maeda Katsuhiro、Steven J. Geib、Dennis P. Curran、Taniguchi Tsuyoshi
  • Journal Title: Angewandte Chemie International Edition Volume: 印刷中 Issue: 19 Pages: 6357-6361
  • DOI: 10.1002/anie.201902001
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Radical trans-Hydroboration of Alkynes with N-Heterocyclic Carbene Boranes (2018)
  • Author(s): Shimoi Masaki、Watanabe Takashi、Maeda Katsuhiro、Dennis P. Curran、Taniguchi Tsuyoshi
  • Journal Title: Angewandte Chemie International Edition Volume: 57 Issue: 30 Pages: 9485-9490
  • DOI: 10.1002/anie.201804515
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Systematic Evaluation of 2-Arylazocarboxylates and 2-Arylazocarboxamides as Mitsunobu Reagents (2018)
  • Author(s): Daisuke Hirose, Martin Gazvoda, Janez Kosmrlj, Tsuyoshi Taniguchi
  • Journal Title: J. Org. Chem. Volume: 83 Issue: 8 Pages: 4712-4729
  • DOI: 10.1021/acs.joc.8b00486
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Recent Advances in Reactions of Heteroatom-Centered Radicals (2017)
  • Author(s): Taniguchi Tsuyoshi
  • Journal Title: Synthesis Volume: 49 Issue: 16 Pages: 3511-3534
  • DOI: 10.1055/s-0036-1588481
  • Peer Reviewed
• [Journal Article] N-Heterocyclic Carbene Boranes are Hydrogen Donors in Masamune?Bergman Reactions of Benzo[3,4]cyclodec-3-ene-1,5-diynes (2017)
  • Author(s): Takashi Watanabe, Steven J. Geib, Dennis P. Curran, Tsuyoshi Taniguchi
  • Journal Title: J. Org. Chem. Volume: 82 Issue: 24 Pages: 13034-13042
  • DOI: 10.1021/acs.joc.7b01981
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Borylative Radical Cyclizations of Benzo[3,4]cyclodec-3-ene-1,5-diynes and N-Heterocyclic Carbene-Boranes (2017)
  • Author(s): Takashi Watanabe, Daisuke Hirose, Dennis P. Curran, Tsuyoshi Taniguchi
  • Journal Title: Chemistry A European Journal Volume: - Issue: 23 Pages: 5404-5409
  • DOI: 10.1002/chem.201700689
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] The “Fully Catalytic System” in Mitsunobu Reaction Has Not Been Realized Yet (2016)
  • Author(s): Daisuke Hirose, Martin Gazvoda, Janez Kosmrlj, Tsuyoshi Taniguchi
  • Journal Title: Organic Letters Volume: 18 Issue: 16 Pages: 4036-4039
  • DOI: 10.1021/acs.orglett.6b01894
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Presentation] N-ヘテロサイクリックカルベン-ボランを用いるプロパギルアセテート誘導体のラジカル的ラクトン化反応 (2019)
  • Author(s): 下井 将輝、前田 勝浩、カラン デニス、谷口 剛史
  • Organizer: 日本化学会第99春季年会(2019)
• [Presentation] Radical borylation of perfluoroarenes with N-heterocyclic carbene-boranes (2019)
  • Author(s): Kosuke Takahashi、Masaki Shimoi、Katsuhiro Maeda、Dennis Curran、Tsuyoshi Taniguchi
  • Organizer: 日本化学会第99春季年会(2019)
• [Presentation] ボリルラジカルを用いるプロパルギルアセテート誘導体のラクトン化反応 (2018)
  • Author(s): 下井 将輝、前田 勝浩、 Dennis P. Curran、谷口 剛史
  • Organizer: 第45回有機典型元素化学討論会
• [Presentation] Radical Reactions of Alkynes with N-Heterocyclic Carbene Boranes (2018)
  • Author(s): Tsuyoshi Taniguchi
  • Organizer: International Congress on Pure & Applied Chemistry (ICPAC) 2018
  • Int'l Joint Research / Invited
• [Presentation] N－ヘテロサイクリックカルベン－ボランを用いるアルキンのラジカル的ヒドロホウ素化反応 (2018)
  • Author(s): 下井 将輝, 渡辺 崇嗣, 谷口 剛史, 前田 勝浩, CURRAN Dennis
  • Organizer: 日本化学会第98春季年会(2018)
• [Presentation] 歪んだジインへのボリルラジカルの付加反応とそれに伴う環化反応 (2017)
  • Author(s): 渡辺 崇嗣, 廣瀨 大祐, 谷口 剛史, Dennis P. CURRAN
  • Organizer: 日本薬学会第137年会
  • Place of Presentation: 東北大学川内北キャンパス（宮城県仙台市）
  • Year and Date: 2017-03-24
• [Presentation] Radical Reactions of Alkynes with N-Heterocyclic Carbene Boranes (2017)
  • Author(s): Tsuyoshi Taniguchi, Takashi Watanabe, Steven J. Geib, Dennis P. Curran, Katsuhiro Maeda
  • Organizer: 3rd International Symposium on Center of Excellence for Innovative Material Sciences Based on Supramolecules
  • Int'l Joint Research
• [Book] e-EROS Encyclopedia of Reagents for Organic Synthesis "Iron Phthalocyanine" (2017)
  • Author(s): Mark W. Zettler, Tsuyoshi Taniguchi
  • Total Pages: 6
  • Publisher: Wiley
  • ISBN: 9780470842898
• [Book] e-EROS Encyclopedia of Reagents for Organic Synthesis "Iron(II) Phthalocyanine" (2016)
  • Author(s): Tsuyoshi Taniguchi
  • Total Pages: 6
  • Publisher: Wiley
• [Remarks] Researcher ID
  • URL: http://www.researcherid.com/rid/D-8414-2015
• [Remarks] ORCID
  • URL: http://orcid.org/0000-0002-4945-480X
• [Remarks] Google scholar citation
  • URL: https://scholar.google.co.jp/citations?user=2xAxhacAAAAJ&hl=ja
• [Remarks] ResearcherID
  • URL: http://www.researcherid.com/rid/D-8414-2015