Functional Ability Elucidation of Auxiliary Light Harvesting Carotenoids Acting in Marine Photosynthesis based on Organic Synthesis

• Project/Area Number: 25410183
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Bio-related chemistry
• Research Institution: Osaka City University
• Principal Investigator: Katsumura Shigeo 大阪市立大学, 大学院理学研究科, 客員教授 (70047364)
• Co-Investigator(Kenkyū-buntansha): SAKAGUCHI KAZUHIKO 大阪市立大学, 大学院理学研究科, 准教授 (80264795)
• Co-Investigator(Renkei-kenkyūsha): HASHIMOTO HIDEKI 大阪市立大学, 複合先端研究機構, 教授 (50222211)
• Project Period (FY): 2013-04-01 – 2016-03-31
• Project Status: Completed (Fiscal Year 2015)
• Budget Amount: ¥5,070,000 (Direct Cost: ¥3,900,000、Indirect Cost: ¥1,170,000); Fiscal Year 2015: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000); Fiscal Year 2014: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000); Fiscal Year 2013: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
• Keywords: 海洋光合成初期過程 / カルボニルカロテノイド / ペリジニン / フコキサンチン / デオキシペリジニン類縁体合成 / 構造的特徴と機能の関係 / 超効率的エネルギー伝達機構解明 / 海洋光合成 / ICT (分子内電荷移動) 準位 / デオキシペリジニン / Pd触媒による３種のカップリング / 立体化学を制御した合成 / 超分子 (PCP) 複合体再構成の試み / 光合成初期過程 / イリデンブテノリド / ICT準位 / 超分子複合体再構成 / 超効率的エネルギー伝達機構 / カロテノイド・ペリジニン / カロテノイド・フコキサンチン / アレン結合 / ３成分連結ワンポットカップリング / アルキニルビニルスズエステル

Outline of Final Research Achievements

Peridinin and fucoxanthin are auxiliary light harvesting pigments in the sea. In the super complexes constructed with these carotenoids, chlorophyll and apoprotain, high (>85%) energy transfer efficiencies from them to chlorophyll were reported. Previously, we substantiated the existence of intramolecular charge transfer state (ICT) by ultrafast time resolved spectra measurements (UTRSM) of the synthesized π-conjugation modified analogues. In this project, we have elucidated that ylidenbutenolide of peridinin is essential for ICT generation and allene of fucoxanthin contributes ICT stabilization, by UTRSM of β-caroten ylidenbutenolide derivatives and also C32 fucoxanthin olefin-derivatives. Intending to reconstitute the corresponding super complex, we have synthesized peridinin decarbonyl analogue by the sequential sp and sp2 couplings from E-β-ethynyl-α-stannyl acrylate, obtained by novel anti-selective ethynylstannylation of propiolate. Reconstitution has not been successful yet.

Research Products

• [Journal Article] Preparation of E-α-stannyl-β-trimethylsilylethynylacrylate, building block for polyconjugated ylidenebutenolide and its derivatives, by novel E-selective ethynylstannylation of propiolate (2016)
  • Author(s): Kinashi, N., Sakaguchi, K., Katsumura, S., Shinada, T.
  • Journal Title: Tetrahedron Letters Volume: 57 Issue: 1 Pages: 129-132
  • DOI: 10.1016/j.tetlet.2015.11.079
  • Peer Reviewed / Open Access
• [Journal Article] Spectroscopic investigation of the carotenoid deoxyperidinin: direct observation of the forbidden S0 → S1 transition (2016)
  • Author(s): Greco, J. A., LaFountain, A. M., Kinashi, N., Shinada, T., Sakaguchi, K., Katsumura, S., S., Magdaong, S., Niedzwiedzki, D.M.R., Birge, R.H., Frank, A.
  • Journal Title: The Journal of Physiological Chemistry B Volume: 120 Issue: 10 Pages: 2731-2734
  • DOI: 10.1021/acs.jpcb.6b00439
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Straightforward synthesis of fucoxanthin short-chain derivatives via modified-Julia olefination (2014)
  • Author(s): Okumura, S.; Kajikawa, T.; Yano, K.; Sakaguchi, K.; Kosumi, D.; Hashimoto, H.; Katsumura, S.
  • Journal Title: Tetrahedron Lett. Volume: 55 Pages: 407-410
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Excited state properties of a short π-electron conjugated peridinin analogue (2014)
  • Author(s): Magdaong, N. M.; Niedzwiedzki, D. M.; Greco, J. A.; Liu, H.; Yano, K.; Kajikawa, T.; Sakaguchi, K.; Katsumura, S.; Birge, R. R.; Frank, H. A.
  • Journal Title: Chem. Phys. Lett. Volume: 593 Pages: 132-139
  • Peer Reviewed
• [Journal Article] Elucidation and Control of an Intramolecular Charge Transfer Property of Fucoxanthin by a Modification of Its Polyene Chain Length (2014)
  • Author(s): Kosumi, D.; Kajikawa T.; Okumura, S.; Sugisaki, M.; Sakaguchi, K.; Katsumura, S.; Hashimoto, H.
  • Journal Title: J. Phys. Chem. Lett. Volume: 5 Pages: 792-797
  • Peer Reviewed
• [Journal Article] Roles of allene-group in an intramolecular charge transfer character of a short fucoxanthin homologue as revealed by femtosecond pump-probe spectroscopy (2014)
  • Author(s): Kosumi, D.; Kajikawa, T.; Yano, K.; Okumura, S.; Sugisaki, M.; Sakaguchi, K.; Katsumura, S.; Hashimoto, H.
  • Journal Title: Chem. Phys. Lett. Volume: 602 Pages: 75-79
  • Peer Reviewed
• [Journal Article] Ultrafast excited state dynamics of marine carotenoid fucoxanthin and its homologues (2014)
  • Author(s): H. Hashimoto, D. Kosumi, R. Fujii, M. Sugisaki, M. Iha, K. Sakaguchi, and S. Katsumura
  • Journal Title: Carotenoid Science Volume: 118 Pages: 4-4
• [Journal Article] Total Syntheses of Zwitterionic Indole Alkaloids, Flavocarpine and Dihydrovincarpine, by Extended Method for Substituted Pyridine Synthesis through Azaelectrocyclization. (2014)
  • Author(s): Hirose, K; Kobayashi, T.; Tsuchikawa, H.; Katsumura, S.
  • Journal Title: Heterocycles Volume: 90 Pages: 150-156
  • Peer Reviewed
• [Journal Article] Straightforward synthesis of fucoxanthin short-chain derivatives via modified-Julia olefination. (2014)
  • Author(s): Okumura, S.; Kajikawa, T.; Yano, K.; Sakaguchi, K.; Kosumi, D.; Hashimoto, H.; Katsumura, S.
  • Journal Title: Tetrahedron Lett. Volume: 55 Pages: 407-410
  • Peer Reviewed
• [Journal Article] Excited state properties of a short π-electron conjugated peridinin analogue. (2014)
  • Author(s): Magdaong, N. M.; Niedzwiedzki, D. M.; Greco, J. A.; Liu, H.; Yano, K.; Kajikawa, T.; Sakaguchi, K.; Katsumura, S.; Birge, R. R.; Frank, H. A.
  • Journal Title: Chem. Phys. Lett. Volume: 593 Pages: 132-139
  • Peer Reviewed
• [Journal Article] Elucidation and Control of an Intramolecular Charge Transfer Property of Fucoxanthin by a Modification of Its Polyene Chain Length. (2014)
  • Author(s): Kosumi, D.; Kajikawa T.; Okumura, S.; Sugisaki, M.; Sakaguchi, K.; Katsumura, S.; Hashimoto, H.
  • Journal Title: J. Phys. Chem. Lett. Volume: 5 Pages: 792-797
  • Peer Reviewed
• [Journal Article] Roles of allene-group in an intramolecular charge transfer character of a short fucoxanthin homologue as revealed by femtosecond pump-probe spectroscopy. (2014)
  • Author(s): Kosumi, D.; Kajikawa, T.; Yano, K.; Okumura, S.; Sugisaki, M.; Sakaguchi, K.; Katsumura, S.; Hashimoto, H.
  • Journal Title: Chem. Phys. Lett. Volume: 594
  • Peer Reviewed
• [Journal Article] Excited States Energies and Dynamics of Peridinin Analogues and the Nature of the Intramolecular Charge Transfer (ICT) State in Carbonyl-Containing Carotenoids. (2013)
  • Author(s): Dariusz, N.; Kajikawa, T.; Aoki, K.; Katsumura, S.; Frank, H.
  • Journal Title: J. Phys. Chem. B Volume: 117 Pages: 6874-6887
  • Peer Reviewed
• [Presentation] Total Synthesis of Paracentrone (2016)
  • Author(s): 西岡勇人、矢野陽、木梨尚人、奥菜津未、鳥山陽平、勝村成雄、品田哲郎、坂口和彦
  • Organizer: 日本化学会第96春季年会
  • Place of Presentation: 同志社大学（京都府・京田辺市）
  • Year and Date: 2016-03-24
• [Presentation] 海洋性カロテノイドであるフコキサンチン類縁体（パラセントロン）のフェムト秒時間分解吸収分光 (2016)
  • Author(s): 橋本秀樹、行平奈央、藤原正澄、西岡勇人、品田哲郎、坂口和彦、勝村成雄
  • Organizer: 日本化学会第96春季年会
  • Place of Presentation: 同志社大学（京都府・京田辺市）
  • Year and Date: 2016-03-24
• [Presentation] 紅色光合成細菌 Rs. rubrum の LH1 サブユニット型複合体とフコキサンチンを用いた再構成LH1 複合体のフェムト秒時間分解吸収分光 (2016)
  • Author(s): 橋本秀樹、行平奈央、須貝祐子、藤原正澄、浦上千藍紗、伊波匡彦、坂口和彦、勝村成雄
  • Organizer: 日本化学会第96春季年会
  • Place of Presentation: 同志社大学（京都府・京田辺市）
  • Year and Date: 2016-03-24
• [Presentation] Total Synthesis of Paracentrone (2016)
  • Author(s): Y. Nishioka, Y. Yano, N. Kinashi, N. Oku, Y. Toriyama, S. Katsumura, T. Shinada, K. Sakaguchi
  • Organizer: The 2016 OCARINA Annual International Meeting
  • Place of Presentation: Osaka City University, Media Center, Osaka
  • Year and Date: 2016-03-17
  • Int'l Joint Research
• [Presentation] Polyfunctional carotenoid synthesis via one-pot strategy: Toward elucidation of highly efficient energy transfer by marine photosynthetic organisms (2015)
  • Author(s): K. Sakaguchi, T. Kajikawa, S. Hananoki, N. Kinashi, D. Kosumi, H. Hashimoto, H. A. Frank, T. Shinada, S. Katsumura
  • Organizer: 2015 International Chemical Congress of Pacific Basin Societies (PACIFICHEM 2015)
  • Place of Presentation: Hawaii Convention Center, Honolulu, Hawaii, USA
  • Year and Date: 2015-12-15
  • Int'l Joint Research
• [Presentation] Total Synthesis of Paracentrone (2015)
  • Author(s): N. Oku, Y. Nishioka, Y. Yano, N. Kinashi, S. Katsumura, T. Shinada, and K. Sakaguchi
  • Organizer: The 19th Osaka City University International Workshop on Advanced Molecular Materials Science
  • Place of Presentation: Osaka City University, Media Center, Osaka
  • Year and Date: 2015-11-12
  • Int'l Joint Research
• [Presentation] Development of E-β-Ethynyl-α-stannylacrylate Toward Efficient Synthesis of Polyfunctional Carotenoids (2015)
  • Author(s): K. Sakaguchi, N. Kinashi, H. A. Frank, S. Katsumura, T. Shinada
  • Organizer: the Twelfth International Kyoto Conference on New Aspects of Organic Chemistry (IKCOC-13)
  • Place of Presentation: Rihga Royal Hotel Kyoto, Kyoto
  • Year and Date: 2015-11-09
  • Int'l Joint Research
• [Presentation] 共役ケトンを有するアポカロテノイドの全合成研究 (2015)
  • Author(s): 西岡勇人、矢野陽、木梨尚人、奥菜津未、鳥山陽平、勝村成雄、品田哲郎、坂口和彦
  • Organizer: 第59回香料・テルペンおよび精油化学に関する討論会
  • Place of Presentation: 近畿大学（大阪府・東大阪市）
  • Year and Date: 2015-09-05
• [Presentation] デオキシペリジニンの合成研究 (2015)
  • Author(s): 坂口和彦、木梨尚人、西岡勇人、奥菜津未、鳥山陽平、H. A. Frank、勝村成雄、品田哲郎
  • Organizer: 第59回香料・テルペンおよび精油化学に関する討論会
  • Place of Presentation: 近畿大学（大阪府・東大阪市）
  • Year and Date: 2015-09-05
• [Presentation] 海洋光合成エネルギー伝達機構の解明に向けた新規多官能性カロテノイドの設計と合成 (2015)
  • Author(s): 坂口和彦、木梨尚人、西岡勇人、奥菜津未、鳥山陽平、H. A. Frank、勝村成雄、品田哲郎
  • Organizer: 第29回カロテノイド研究談話会
  • Place of Presentation: 首都大学東京（東京都・八王子市）
  • Year and Date: 2015-09-04
• [Presentation] Development of Novel E-β-Ethynylvinylstannane for Cross Coupling Reaction and Efficient Synthesis of Peridinin Derivatives (2015)
  • Author(s): 木梨尚人・坂口和彦・品田哲郎・勝村成雄
  • Organizer: 日本化学会第95春季年会
  • Place of Presentation: 日本大学・船橋キャンパス（千葉県船橋市）
  • Year and Date: 2015-03-26 – 2015-03-29
• [Presentation] Synthetic Study of Paracentrone using Cross Coupling Method (2015)
  • Author(s): Y. Nishioka, N. Kinashi, K. Sakaguchi, T. Shinada and S. Katsumura
  • Organizer: The 18th Osaka City University International Conference
  • Place of Presentation: Osaka City University, Media Center（大阪府大阪市）
  • Year and Date: 2015-03-09
• [Presentation] Direct Preparation of E-beta-Ethynyl-alpha-stannylacrylate as Effective Building Block for Peridinin Synthesis by Novel E-Selective Ethynylstannylation of Propiolate (2015)
  • Author(s): N. Kinashi, K. Sakaguchi, T. Shinada and S. Katsumura
  • Organizer: The 18th Osaka City University International Conference
  • Place of Presentation: Osaka City University, Media Center（大阪府大阪市）
  • Year and Date: 2015-03-09
• [Presentation] Direct Preparation of E-beta-Ethynyl-alpha-stannylacrylate as Effective Building Block for Peridinin Synthesis by Novel E-Selective Ethynylstannylation of Propiolate (2015)
  • Author(s): N. Kinashi, K. Sakaguchi, T. Shinada and S. Katsumura
  • Organizer: The 2014 OCARINA Annual International Meeting
  • Place of Presentation: Osaka City University, Media Center（大阪府大阪市）
  • Year and Date: 2015-03-04 – 2015-03-05
• [Presentation] クロスカップリングに有用な新規アルキニルスズの開発とペリジニン類の効率的合成研究 (2014)
  • Author(s): 木梨尚人・坂口和彦・小澄大輔・橋本秀樹・品田哲郎・勝村成雄
  • Organizer: 第58回香料・テルペンおよび精油化学に関する討論会
  • Place of Presentation: 和歌山大学（和歌山県和歌山市）
  • Year and Date: 2014-09-20 – 2014-09-22
• [Presentation] イリデンブテノリドを骨格に含むカロテノイド類の合成と励起エネルギー準位特性 (2014)
  • Author(s): 坂口和彦・梶川敬之・矢野恒記・長谷川愼二・花ノ木祥平・小澄大輔・橋本秀樹・H. A. Frank・木梨尚人・品田哲郎・勝村成雄
  • Organizer: 第28回カロテノイド研究談話会
  • Place of Presentation: 石川県文教会館（石川県金沢市）
  • Year and Date: 2014-09-04 – 2014-09-05
• [Presentation] 新規アンチ挿入型エチニルスタニル化反応の開発とペリジニン骨格ワンポット合成への展開 (2014)
  • Author(s): 木梨尚人・坂口和彦・品田哲郎・勝村成雄
  • Organizer: 第34回有機合成若手セミナー
  • Place of Presentation: 大阪大学豊中キャンパス（大阪府豊中市）
  • Year and Date: 2014-08-05
• [Presentation] Elucidation and Control of Ultrafast Intramolecular Charge Transfer Dynamics of Marine Photosynthetic Pigments (2014)
  • Author(s): D. Kosumi, T. Kajikawa, K. Yano, S. Okumura, M. Sugisaki, K. Sakaguchi, S. Katsumura, H. Hashimoto
  • Organizer: 19th International Conference on Ultrafast Phenomena
  • Place of Presentation: Okinawa Convention Center, Naha（沖縄県那覇市）
  • Year and Date: 2014-07-07 – 2014-07-11
• [Presentation] Ultrafast excited state dynamics of marine carotenoid fucoxanthin and its homologues (2014)
  • Author(s): Hideki Hashimoto, Daisuke Kosumi, Ritsuko Fujii, Mitsuru Sugisaki, Masahiko Iha, Kazuhiko Sakaguchi, and Shigeo Katsumura
  • Organizer: 17th International Symposium on Carotenoids
  • Place of Presentation: Park City, Utah（Utah, USA）
  • Year and Date: 2014-06-29 – 2014-07-04
• [Presentation] ペリジニン、フコキサンチン類縁体合成と光合成を担うエネルギー準位の性質 (2014)
  • Author(s): 梶川敬之・矢野恒記・小澄大輔・橋本秀樹・H. A. Frank・坂口和彦・木梨尚人・品田哲郎・勝村成雄
  • Organizer: 日本化学会第94春季年会
  • Place of Presentation: 名古屋大学・東山キャンパス
• [Presentation] ペリジニンおよびフコキサンチン類縁体の合成と光合成を担うエネルギー準位の性質 (2013)
  • Author(s): 矢野恒記・梶川敬之・奥村聡・小澄大輔・橋本秀樹・H. A. Frank・坂口和彦・品田哲郎・勝村成雄
  • Organizer: 第57回香料・テルペンおよび精油化学に関する討論会
  • Place of Presentation: 埼玉大学
• [Presentation] One-pot Asymmetric Azaelectrocyclization as Strategy for Alkaloid Synthesis: Total synthesis of Protoemetine (2013)
  • Author(s): Okuno, Y.; Takeuchi, Y.; Kobayashi, S.; Sakaguchi, T.; Tsuchikawa, H.; Katsumura, S.
  • Organizer: The Eighth International Symposium on Integrated Synthesis (ISIS-8)
  • Place of Presentation: Todaiji Temple Cultural Center, Nara, Japan
• [Presentation] Polyfunctional Carotenoid Synthesis via One-pot Strategy: Toward Elucidation of Energy Transfer Process in Marine Photosynthesis (2013)
  • Author(s): Kajikawa, T.; Yano, K.; Hananoki, S.; Hasegawa, S.; Sakaguchi, K.; Shinada, T.; Katsumura, S.
  • Organizer: The Eighth International Symposium on Integrated Synthesis (ISIS-8)
  • Place of Presentation: Todaiji Temple Cultural Center, Nara, Japan
• [Presentation] Synthesis of Sphingolipid Derivatives as Effective Tool Molecules
  • Author(s): 勝村成雄
  • Organizer: タンパク質情報交換会
  • Place of Presentation: 大阪大学理学部
  • Invited
• [Presentation] 天然物合成の魔力に４０年
  • Author(s): 勝村成雄
  • Organizer: 理研シンポジウム
  • Place of Presentation: 大阪大学会館講堂
  • Invited
• [Presentation] 機能性天然物合成とカップリング反応
  • Author(s): 勝村成雄
  • Organizer: 近畿化学協会有機金属部会 平成２５年度第２回例会
  • Place of Presentation: 早稲田大学西早稲田キャンパス
  • Invited
• [Presentation] 天然物合成の魔力に４０年
  • Author(s): 勝村成雄
  • Organizer: 関西創農薬研究会
  • Place of Presentation: 住友化学宝塚 健康・農薬研究所
  • Invited
• [Presentation] 天然物合成の魔力に４０年：機能解明に向けた有機合成からのアプローチ
  • Author(s): 勝村成雄
  • Organizer: 平成２５年度 徳島文理大学薬学部学術講演会
  • Place of Presentation: 徳島文理大学
  • Invited