Development of Highly Electron-Accepting Diphosphene Ligands and Application to the Synthesis of Helical Molecules in Optically Active Form

• Project/Area Number: 16H07126
• Research Category: Grant-in-Aid for Research Activity Start-up
• Allocation Type: Single-year Grants
• Research Field: Organic chemistry
• Research Institution: Osaka Prefecture University
• Principal Investigator: Tsurusaki Akihiro 大阪府立大学, 理学(系)研究科(研究院), 助教 (40623848)
• Project Period (FY): 2016-08-26 – 2018-03-31
• Project Status: Completed (Fiscal Year 2017)
• Budget Amount: ¥2,990,000 (Direct Cost: ¥2,300,000、Indirect Cost: ¥690,000); Fiscal Year 2017: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000); Fiscal Year 2016: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
• Keywords: リン / ジホスフェン / 遷移金属錯体 / 触媒反応 / 軸不斉 / 光学活性 / 1,1’-ビナフチル / 金 / 遷移金属 / 有機合成化学 / 電子受容性配位子 / 分子内環化反応

Outline of Final Research Achievements

We succeeded in the synthesis of the new diphosphene having the P=P double-bond, which is expected to have the high electron-accepting character, and 1,1’-binaphthyl group with the axial chirality in both racemic and enantiomerically pure forms. Spectroscopic analyses, X-ray crystallographic analysis, and theoretical calculations revealed their structures, properties, and isomerization behavior among four stereoisomers. Furthermore, the corresponding diphosphene-gold(I) complex was isolated and utilized as a catalyst for the intramolecular hydroarylation reaction of aryl butynyl ether.

Research Products

• [Journal Article] 1,1’-Binaphthyl-substituted Diphosphene: Synthesis, Structures, and Chiral Optical Properties (2018)
  • Author(s): Tsurusaki, A.; Ura, R.; Kamikawa, K.
  • Journal Title: Dalton Trans. Volume: 47 Issue: 13 Pages: 4437-4441
  • DOI: 10.1039/c8dt00441b
  • Peer Reviewed
• [Journal Article] Syntehsis, Structures, and Properties of Hexapole Helicenes: Assembling Six [5]Helicene Substructures into Highly Twisted Aromatic Systems (2017)
  • Author(s): Hosokawa, T.; Takahashi, Y.; Matsushima, T.; Watanabe, S.; Kikkawa, S.; Azumaya, I.; Tsurusaki, A.; Kamikawa, K.
  • Journal Title: J. Am Chem. Soc. Volume: 139 Issue: 51 Pages: 18512-18521
  • DOI: 10.1021/jacs.7b07113
  • Peer Reviewed
• [Journal Article] Synthesis and structures of lithium alkoxytris(dimethylphenylsilyl)borates (2017)
  • Author(s): Akihiro Tsurusaki, Keisuke Yoshida, Soichiro Kyushin
  • Journal Title: Dalton Trans. Volume: 46 Issue: 27 Pages: 8705-8708
  • DOI: 10.1039/c7dt00395a
  • Peer Reviewed
• [Journal Article] Synthesis, Structures, and Electronic Properties of Dithienosiloles Bearing Bulky Aryl Groups: Conjugation between a pi-Electron System and “Perpendicular” Aryl Groups (2017)
  • Author(s): Akihiro Tsurusaki, Atsushi Kobayashi, Soichiro Kyushin
  • Journal Title: Asian. J. Org. Chem. Volume: 6 Issue: 6 Pages: 737-745
  • DOI: 10.1002/ajoc.201700058
  • Peer Reviewed
• [Journal Article] Decasilahexahydrotriquinacene and Decasilaisotwistane: σConjugation on a Bowl Surface (2017)
  • Author(s): Akihiro Tsurusaki, Yu Koyama, Soichiro Kyushin
  • Journal Title: J. Am. Chem. Soc. Volume: 139 Issue: 11 Pages: 3982-3985
  • DOI: 10.1021/jacs.7b00250
  • Peer Reviewed
• [Presentation] [5]および[7]ヘリセン構造を有する六重ヘリセンに関する合成、および理論化学的考察 (2018)
  • Author(s): 細川 朋佳・麻田 俊雄・津留崎 陽大・神川 憲
  • Organizer: 日本化学会第98春季年会(2018)
• [Presentation] 軸不斉ビナフチル置換ジホスフェンの光学特性 (2018)
  • Author(s): 浦 里華子・津留崎 陽大・神川 憲
  • Organizer: 日本化学会第98春季年会(2018)
• [Presentation] 面不斉金属錯体を基盤とするホスフィン‐オレフィン配位子の合成と不斉触媒反応への応用 (2018)
  • Author(s): 大矢 直輝・曾 雅怡・津留崎 陽大・神川 憲
  • Organizer: 日本化学会第98春季年会(2018)
• [Presentation] 1,1'-ビナフチル置換ジホスフェンの合成 (2017)
  • Author(s): 浦 里華子・津留崎 陽大・神川 憲
  • Organizer: 日本化学会第97春季年会(2017)
  • Place of Presentation: 慶應義塾大学日吉キャンパス
  • Year and Date: 2017-03-16
• [Presentation] [5]ヘリセン誘導体の[2+2+2]環化三量化反応による六重ヘリセンの合成と物性 (2017)
  • Author(s): 細川朋佳・津留崎陽大・神川憲
  • Organizer: 日本化学会第97春季年会(2017)
  • Place of Presentation: 慶應義塾大学日吉キャンパス
  • Year and Date: 2017-03-16
• [Presentation] 6 つの[5]ヘリセン骨格を持つ六重ヘリセンの熱異性化挙動 (2017)
  • Author(s): 細川朋佳・津留崎陽大・神川憲
  • Organizer: 日本化学会第97春季年会(2017)
  • Place of Presentation: 慶應義塾大学日吉キャンパス
  • Year and Date: 2017-03-16
• [Presentation] 面不斉金属錯体を基盤とするホスフィン‐オレフィン配位子の合成と不斉触媒反応への応用 (2017)
  • Author(s): 大矢 直輝・曾 雅怡・津留崎 陽大・神川 憲
  • Organizer: 日本化学会第97春季年会(2017)
  • Place of Presentation: 慶應義塾大学日吉キャンパス
  • Year and Date: 2017-03-16
• [Presentation] 大きなねじれ構造を有する六重ヘリセンの合成、および物性 (2017)
  • Author(s): 細川朋佳・高橋裕輔・松島智也・吉川晶子・東屋功・渡邊総一郎・津留崎陽大・神川憲
  • Organizer: 第28回基礎有機化学討論会
• [Presentation] 1,1'-ビナフチル置換ジホスフェンとその金(I)錯体の合成と構造 (2017)
  • Author(s): 浦 里華子・津留崎 陽大・神川 憲
  • Organizer: 第64回有機金属化学討論会
• [Presentation] 面不斉ハーフメタロセン配位子を活用した不斉触媒反応 (2017)
  • Author(s): 大矢直輝・曽雅怡・津留崎陽大・神川憲
  • Organizer: 第120回触媒討論会
• [Presentation] 1,1'-ビナフチル置換ジホスフェンと錯形成 (2017)
  • Author(s): 浦 里華子・津留崎 陽大・神川 憲
  • Organizer: 第7回CSJ化学フェスタ2017
• [Presentation] Synthesis and Structures of 1,1’-Binaphthyl-Substituted Diphosphene and its Gold(I) Complex (2017)
  • Author(s): Rikako Ura, Akihiro Tsurusaki, Ken Kamikawa
  • Organizer: Joint Symposium of Asia Five Universities
  • Int'l Joint Research
• [Presentation] Synthesis and Properties of Hexapole Helicenes with Highly Distorted Structures (2017)
  • Author(s): Tomoka Hosokawa, Yusuke Takahashi, Tomoya Matsushima, Soichiro Watanabe, Shoko Kikkawa, Isao Azumaya, Akihiro Tsurusaki, Ken Kamikawa
  • Organizer: Joint Symposium of Asia Five Universities
  • Int'l Joint Research
• [Presentation] Synthesis of Binaphthyl-Substituted Diphosphenes (2016)
  • Author(s): Rikako Ura, Akihiro Tsurusaki, Ken Kamikawa
  • Organizer: The 3rd Joint Symposium of NTUT, NTNU, and OPU on Chemistry
  • Place of Presentation: Osaka Prefecture University, I-site Namba
  • Year and Date: 2016-09-05
• [Presentation] Synthesis of Hexapole Helicenes by Palladium-Catalyzed [2+2+2] Cyclization Reactions (2016)
  • Author(s): Tomoka Hosokawa, Akihiro Tsurusaki, Ken Kamikawa
  • Organizer: The 3rd Joint Symposium of NTUT, NTNU, and OPU on Chemistry
  • Place of Presentation: Osaka Prefecture University, I-site Namba
  • Year and Date: 2016-09-05