Cage-Shaped Phosphite: Precise Control of Its Lewis Basicity and Construction of Peculiar Reaction Field

• Project/Area Number: 16K21137
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Multi-year Fund
• Research Field: Organic chemistry; Synthetic chemistry
• Research Institution: Osaka University
• Principal Investigator: KONISHI Akihito 大阪大学, 工学研究科, 助教 (10756480)
• Project Period (FY): 2016-04-01 – 2018-03-31
• Project Status: Completed (Fiscal Year 2017)
• Budget Amount: ¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000); Fiscal Year 2017: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000); Fiscal Year 2016: ¥2,340,000 (Direct Cost: ¥1,800,000、Indirect Cost: ¥540,000)
• Keywords: ルイス塩基性 / カゴ型配位子 / 金属配位子 / π共役系 / ルイス塩基 / 合成化学

Outline of Final Research Achievements

Electronic and/or steric factors can influence the chemical reactivity and molecular recognition. The sterically controlled cage-shaped phosphites were synthesized and successfully characterized by single-crystal X-ray analysis. The Lewis basicity of the phosphorus atom in the cage-shaped phosphites was determined by coupling constant (31P-77Se) after selenium oxidation. To investigate the reactivity of the obtained cage-shaped phosphites, some palladium-catalyzed reactions were performed and their results were compared with conventional phosphine or phosphite ligands.

Research Products

• [Journal Article] 1,8-Diphenyl-9,10-Bis(arylethynyl)phenanthrenes: Synthesis, Distorted Structure, and Optical Properties (2018)
  • Author(s): Konishi Akihito、Morinaga Atsushi、Fukuhara Gaku、Nishijima Masaki、Mori Tadashi、Kida Toshiyuki、Yasuda Makoto
  • Journal Title: Chemistry A European Journal Volume: 印刷中 Issue: 25 Pages: 6625-6631
  • DOI: 10.1002/chem.201800150
  • Peer Reviewed / Open Access
• [Journal Article] Benzenoid Quinodimethanes (2017)
  • Author(s): Konishi, Akihito; Kubo, Takashi
  • Journal Title: Top. Curr. Chem. Volume: 375 Issue: 6 Pages: 1-37
  • DOI: 10.1007/s41061-017-0171-2
  • Peer Reviewed
• [Journal Article] Synthesis and Characterization of Dibenzo[a,f]pentalene: Harmonization of the Antiaromatic and Singlet Biradical Character (2017)
  • Author(s): Akihito Konishi, Yui Okada, Motohiro Nakano, Kenji Sugisaki, Kazunobu Sato, Takeji Takui, and Makoto Yasuda
  • Journal Title: J. Am. Chem. Soc. Volume: 139 Issue: 43 Pages: 15284-15287
  • DOI: 10.1021/jacs.7b05709
  • Peer Reviewed
• [Journal Article] Anthroxyl-based biradical: toward the construction of highly stable multi-spin systems (2017)
  • Author(s): Yasukazu Hirao, Akihito Konishia, Takashi Kubo
  • Journal Title: Org. Chem. Front. Volume: 印刷中 Issue: 5 Pages: 828-838
  • DOI: 10.1039/c7qo00130d
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Tuning Lewis Acidity by a Transannular pπ--σ* Interaction between Boron and Silicon/Germanium Atoms Supported by a Cage-Shaped Framework (2017)
  • Author(s): Akihito Konishi, Koichi Nakaoka, Hideto Nakajima, Kouji Chiba, Akio Baba, Makoto Yasuda
  • Journal Title: Chemistry - A European Journal Volume: 印刷中 Issue: 22 Pages: 5219-5223
  • DOI: 10.1002/chem.201700659
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] C3-Symmetric Boron Lewis Acid with a Cage-Shape for Chiral Molecular Recognition and Asymmetric Catalysis (2017)
  • Author(s): Akihito Konishi, Koichi Nakaoka, Hikaru Maruyama, Hideto Nakajima, Tomohiro Eguchi, Akio Baba, and Makoto Yasuda
  • Journal Title: Chem. Eur. J. Volume: 23 Issue: 6 Pages: 1273-1277
  • DOI: 10.1002/chem.201605712
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Synthesis and Characterization of Sterically Crowded Aryloxides: 'Mitsubishi'-Class of Tetrametallic Aluminum Complexes (2017)
  • Author(s): Akihito Konishi, Hideto Nakajima, Hikaru Maruyama, Sachiko Yoshioka, Akio Baba, and Makoto Yasuda
  • Journal Title: Polyhedron Volume: 125 Pages: 130-134
  • DOI: 10.1016/j.poly.2016.10.019
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Tautomerization and Dimerization of 6,13-Disubstituted Derivatives of Pentacene (2017)
  • Author(s): Akihito Konishi, Andreas Waterloo, Yong Liang, Yang Cao, Constantin Hetzer, Dan Lehnherr, Frank Hampel, Kendall N. Houk, Rik R. Tykwinski
  • Journal Title: Chemistry - A European Journal Volume: 印刷中 Issue: 25 Pages: 6111-6117
  • DOI: 10.1002/chem.201604099
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] First Isolation and Characterization of the Highly Coordinated Group 14 Enolates; Effects of the Coordination Controls on the Geometry and Tautomerization of Germyl Enolates (2016)
  • Author(s): Akihito Konishi, Yohei Mimani, Takahisa Hosoi, Kouji Chiba, and Makoto Yasuda
  • Journal Title: Chem. Eur. J. Volume: 22 Issue: 36 Pages: 12688-12691
  • DOI: 10.1002/chem.201603147
  • Peer Reviewed / Acknowledgement Compliant
• [Presentation] カゴ型ホスファイトの合成と反応への応用 (2018)
  • Author(s): 小西 彬仁・富田 和馬・安田 誠
  • Organizer: 日本化学会第98春季年会
• [Presentation] ホウ素原子周りの環境制御に基づくカゴ型ホウ素錯体の性状調節とルイス酸触媒としての展開 (2018)
  • Author(s): 小西 彬仁・田中 大貴・安田 誠
  • Organizer: 日本化学会第98春季年会
• [Presentation] Utilization of Chelated Germyl Enolates toward Synthesis of Functionalized Compounds: Diastereoselective Aldol Reaction and Transformation of Germanium-Carbon Bond (2018)
  • Author(s): MINAMI, Yohei; KONISHI, Akihito; YASUDA, Makoto
  • Organizer: The 98th CSJ Annual Meeting
• [Presentation] ヘプタレン骨格を組み込んだ平面縮合多環式炭化水素の合成と物性 (2018)
  • Author(s): 小西 彬仁・掘井 康稀・安田 誠
  • Organizer: 日本化学会第98春季年会
• [Presentation] Synthesis and Properties of π-Extended Dibenzo[a,f]pentalenes: Effect of Ring-annulation on the Open-shell and Antiaromatic Character (2018)
  • Author(s): KONISHI, Akihito; Okada, Yui; YASUDA, Makoto
  • Organizer: The 98th CSJ Annual Meeting
• [Presentation] Diastereoselective Aldol Reaction of Cyclic Germanium Enolates from α,β-Unsaturated Ketones with Ge(II) Salt and its Application to Synthesis of Functionalized Compounds (2017)
  • Author(s): KONISHI, Akihito; MINAMI, Yohei; YASUDA, Makoto
  • Organizer: The 97th CSJ Annual Meeting
  • Place of Presentation: 慶応義塾大学
  • Year and Date: 2017-03-16
• [Presentation] 集積四置換フェナントレン誘導体の合成と物性およびその反応性 (2017)
  • Author(s): 小西 彬仁・森永 充志・安田 誠
  • Organizer: 日本化学会第97春季年会
  • Place of Presentation: 慶応義塾大学
  • Year and Date: 2017-03-16
• [Presentation] ジベンゾ[a,f]ペンタレンの合成と物性 (2017)
  • Author(s): 小西 彬仁・岡田 優衣・中野 元裕・杉崎 研司・佐藤 和信・工位 武治・安田 誠
  • Organizer: 日本化学会第97春季年会
  • Place of Presentation: 慶応義塾大学
  • Year and Date: 2017-03-16
• [Presentation] ジナフト[a,f]ペンタレンの合成と物性 (2017)
  • Author(s): 小西 彬仁・岡田 優衣・安田 誠
  • Organizer: 日本化学会第97春季年会
  • Place of Presentation: 慶応義塾大学
  • Year and Date: 2017-03-16
• [Presentation] ゲルマニウムエノラートの構造と反応性および多官能性化合物への合成展開 (2017)
  • Author(s): 南 陽平・小西 彬仁・安田 誠
  • Organizer: 第111回有機合成シンポジウム
• [Presentation] π拡張フェナントレンの合成と物性および反応性 (2017)
  • Author(s): 小西 彬仁・森永 充志・安田 誠
  • Organizer: 第37回有機合成若手セミナー
• [Presentation] ジベンゾ[a,f]ペンタレンの合成と開殻性及び反芳香族性の評価 (2017)
  • Author(s): 小西 彬仁・岡田 優衣・安田 誠
  • Organizer: 第37回有機合成若手セミナー
• [Presentation] α,β-不飽和ケトン由来のキレート型ゲルミルエノラートの反応性と官能性化合物への変換 (2017)
  • Author(s): 南 陽平・小西 彬仁・安田 誠
  • Organizer: 第65回有機金属化学討論会
• [Presentation] 平面に固定化されたπ拡張ヘプタレンの合成 (2017)
  • Author(s): 小西 彬仁・掘井 康稀・安田 誠
  • Organizer: 第29回基礎有機化学討論会
• [Presentation] 複数のハロゲン原子を導入したカゴ型ホウ素錯体の合成と性質 (2017)
  • Author(s): 小西 彬仁・田中 大貴・安田 誠
  • Organizer: 第29回基礎有機化学討論会
• [Presentation] 近接したフェニル基とエチニル基間の酸化的環化反応と縮合多環式カチオンの合成 (2017)
  • Author(s): 小西 彬仁・森永 充志・安田 誠
  • Organizer: 第29回基礎有機化学討論会
• [Presentation] π拡張[a,f]縮環ペンタレン誘導体の合成と物性 (2017)
  • Author(s): 小西 彬仁・岡田 優衣・安田 誠
  • Organizer: 第29回基礎有機化学討論会
• [Presentation] Synthesis and Electronic Structure of Dibenzo[a,f]pentalene (2017)
  • Author(s): Akihito Konishi, Yui Okada, Motohiro Nakano, Kenji Sugisaki, Kazunobu Sato, Takeji Takui, and Makoto Yasuda
  • Organizer: The 5th AWEST 2017
  • Int'l Joint Research / Invited
• [Presentation] Dibenzo[a,f]pentalene: A π-Electronc System with Antiaromatic and Singlet Biradical Character (2017)
  • Author(s): Akihito Konishi, Yui Okada, Motohiro Nakano, Kenji Sugisaki, Kazunobu Sato, Takeji Takui, and Makoto Yasuda
  • Organizer: The 11th Japanese-Russian workshop
  • Int'l Joint Research / Invited
• [Presentation] First Characterization of Highly Coordinated Group 14 Enolates and Tautomeric Behavior of Germyl Enolates (2016)
  • Author(s): Akihito Konishi, Yohei Minami, and Makoto Yasuda
  • Organizer: The 10th International Symposium on Integrated Synthesis
  • Place of Presentation: Awaji, Japan
  • Year and Date: 2016-11-18
  • Int'l Joint Research
• [Presentation] カゴ型構造規制によるアルミニウムのルイス酸性制御と基質選択的なルイス酸触媒反応への展開 (2016)
  • Author(s): 小西 彬仁・西村 聡汰・安田 誠
  • Organizer: 第6回CSJフェスタ2016
  • Place of Presentation: タワーホール船堀
  • Year and Date: 2016-11-14
• [Presentation] ゲルミルエノラートの構造と互変異性の機構 (2016)
  • Author(s): 小西 彬仁・南 陽平・安田 誠
  • Organizer: 第63回有機金属化学討論会
  • Place of Presentation: 早稲田大学
  • Year and Date: 2016-09-14
• [Presentation] 近接したフェニル基を有するエチニルフェナントレン誘導体の合成と物性 (2016)
  • Author(s): 小西 彬仁・森永充志・安田 誠
  • Organizer: 第27回基礎有機化学討論会
  • Place of Presentation: 広島国際会議場
  • Year and Date: 2016-09-01
• [Presentation] インジウム塩による炭素‐炭素結合形成反応を利用したas-ジベンゾペンタレンの合成 (2016)
  • Author(s): 小西 彬仁・岡田 優衣・安田 誠
  • Organizer: 第27回基礎有機化学討論会
  • Place of Presentation: 広島国際会議場
  • Year and Date: 2016-09-01
• [Presentation] Syntheses, Structures and Optical Properties of Phenathrene Derivatives (2016)
  • Author(s): Akihito Konishi, Atsushi Morinaga, and Makoto Yasuda
  • Organizer: International Symposium on Homogeneous Catalysis
  • Place of Presentation: Kyoto, Japan
  • Year and Date: 2016-07-11
  • Int'l Joint Research
• [Remarks] 大阪大学研究者総覧
  • URL: http://www.dma.jim.osaka-u.ac.jp/view?l=ja&u=10002506&i=j9&kc=1&o=name-a&pp=50&oo=1000043&sm=name&sl=ja&sp=1#header
• [Remarks] 大阪大学大学院工学研究科応用化学専攻安田研ホームページ
  • URL: http://www.chem.eng.osaka-u.ac.jp/~yasuda-lab/
• [Remarks] 大阪大学大学院工学研究科応用化学専攻 安田研究室
  • URL: http://www.chem.eng.osaka-u.ac.jp/~yasuda-lab/
• [Remarks] 大阪大学 研究者総覧
  • URL: http://www.dma.jim.osaka-u.ac.jp/view?l=ja&u=10002506&i=j9&kc=1&o=name-a&pp=50&oo=1000043&sm=name&sl=ja&sp=1