Dehydrative Formation and Transformation of Amino Acid Derivatives Using Well-designed Hydrogen Transfer Catalysts

• Project Area: Precise Formation of a Catalyst Having a Specified Field for Use in Extremely Difficult Substrate Conversion Reactions
• Project/Area Number: 16H01012
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Nagoya University
• Principal Investigator: 斎藤 進 名古屋大学, 理学研究科, 教授 (90273268)
• Project Period (FY): 2016-04-01 – 2018-03-31
• Project Status: Completed (Fiscal Year 2017)
• Budget Amount: ¥5,720,000 (Direct Cost: ¥4,400,000、Indirect Cost: ¥1,320,000); Fiscal Year 2017: ¥2,860,000 (Direct Cost: ¥2,200,000、Indirect Cost: ¥660,000); Fiscal Year 2016: ¥2,860,000 (Direct Cost: ¥2,200,000、Indirect Cost: ¥660,000)
• Keywords: アミド化 / ジボラン / 芳香族カルボン酸 / アミン / 分子触媒 / アミノ酸 / ペプチド / カルボン酸 / アミド / 水素移動 / 環状ホスファゼン / オキサゾリン / 脱水 / 精密水素移動場 / ルテニウム錯体触媒 / トリフォスファゼン / 修飾アミノ酸

Outline of Annual Research Achievements

近年，非天然（環状）ペプチドの医薬としての潜在性が再発掘され，その大量供給法の必要性が格段に増しつつある．塩廃棄物を極力抑えた「ゼロエミッション型」に基づくペプチドや修飾アミノ酸の触媒的な合成法および変換法の基盤の確立は，学術面や実用面，および工業面でも大きな進展をもたらす．このような背景のもと、「脱水」のみを伴う，ペプチド（アミド）基形成法は魅力的な方法である．H29年度に新たに注目したのは，アミド化の触媒開発における単純なジボラン構造に基づく触媒設計指針である．脂肪族カルボン酸よりも酸性の高い（従って相当するカルボン酸アミン塩が生成しアミド化が進行しにくい）安息香酸とベンジルアミンをモデル基質として選びアミド化反応を検討した．様々なL2B-BL2構造を触媒前駆体（1 mol%）として使用したところ，ある種のL2B-BL2を用いた場合，これら基質間での脱水的アミド化反応が円滑に進行し，N-ベンジルベンズアミドをほぼ定量的に得た．それ以外の様々な芳香族カルボン酸とアミンとの脱水的アミド基形成にも有効である．L2B-BL2をカルボン酸のみと混合した場合，もしくはアミンとカルボン酸の両者と混合したところいずれの場合も，L2B-BL2とカルボン酸との選択的な相互作用による四配位ボラン構造が確認された．また，L2B-BL2とカルボン酸が相互作用した中間体もESI-MS分析で確認された．L2B-BL2骨格はカルボキシラートに選択的に配位できるため，それ以外の官能基との相互作用が比較的避けられることによる「官能基選択性・許容性」の面で十分なポテンシャルがあることが示された．芳香族カルボン酸だけではなく，脂肪族カルボン酸でも問題なくアミド基形成が進行し基質適用範囲も広い．

Research Progress Status

29年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

29年度が最終年度であるため、記入しない。

Research Products

• [Int'l Joint Research] Meunster University(Germany)
• [Int'l Joint Research] Queens University(Canada)
• [Journal Article] Photocatalytic hydrogenolysis of allylic alcohols for rapid access to platform chemicals and fine chemicals (2018)
  • Author(s): Takada Yuki、Caner Joaquim、Naka Hiroshi、Saito Susumu
  • Journal Title: Pure Appl. Chem. Volume: 90 Issue: 1 Pages: 167-174
  • DOI: 10.1515/pac-2017-0501
  • Peer Reviewed / Open Access
• [Journal Article] Photocatalytic Transfer Hydrogenolysis of Allylic Alcohols on Pd/TiO2: A Shortcut to (S)-(+)-Lavandulol (2017)
  • Author(s): Takada Yuki、Caner Joaquim、Kaliyamoorthy Selvam、Naka Hiroshi、Saito Susumu
  • Journal Title: Chem. Eur. J. Volume: 23 Issue: 71 Pages: 18025-18032
  • DOI: 10.1002/chem.201704099
  • Peer Reviewed / Open Access
• [Journal Article] Catalytic transformation of functionalized carboxylic acids using multifunctional rhenium complexes (2017)
  • Author(s): Naruto Masayuki、Agrawal Santosh、Toda Katsuaki、Saito Susumu
  • Journal Title: Sci. Rep. Volume: 7 Issue: 1 Pages: 3425-3425
  • DOI: 10.1038/s41598-017-03436-y
  • Peer Reviewed / Open Access
• [Journal Article] Multifaceted catalytic hydrogenation of amides via diverse activation of a sterically confined bipyridine-ruthenium framework (2017)
  • Author(s): Takashi Miura, Masayuki Naruto, Katsuaki Toda, Taiki Shimomura, Susumu Saito
  • Journal Title: Sci. Rep. (Springer Nature) Volume: to be determined Issue: 1 Pages: 1586-1586
  • DOI: 10.1038/s41598-017-01645-z
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Dehydrogenation of Primary Aliphatic Alcohols by Au/TiO2 Photocatalysts (2017)
  • Author(s): Masaki Shibata, Ryoko Nagata, Susumu Saito, Hiroshi Naka
  • Journal Title: Chem. Lett. Volume: 46 Issue: 4 Pages: 580-582
  • DOI: 10.1246/cl.161195
  • NAID: 130005549078
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Stereoselective synthesis of cis, cis-configured perhydroquinoxaline-5-carbonitrile from cyclohex-2-en-1-ol (2016)
  • Author(s): Adrian Schulte, Susumu Saito, Bernhard Weunsch
  • Journal Title: J. Heterocycl. Chem. Volume: 53 Issue: 2 Pages: 533-536
  • DOI: 10.1002/jhet.2322
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Investigation of the Corey Bromolactamization with N-Functionalized Allylamines (2016)
  • Author(s): Adrian Schulte, Simon Janich, Ernst-Ulrich Weuthwein, Susumu Saito, Bernhard Weunsch
  • Journal Title: J. Heterocycl. Chem. Volume: 53 Issue: 6 Pages: 1827-1837
  • DOI: 10.1002/jhet.2493
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Synthesis of morphan derivatives with additional substituents in 8-position (2016)
  • Author(s): Janine Stefaowitz, Dirk Schepmann, Constantin Daniliuc, Susumu Saito, Bernhard Weunsch
  • Journal Title: Zeitschrift feur Naturforschung B Volume: 71 Issue: 10 Pages: 1057-1069
  • DOI: 10.1515/znb-2016-0129
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Versatile Ruthenium Complex “RuPCY” for Directed Catalytic Hydrogen Management in Organic Synthesis (2016)
  • Author(s): uki Takada, Megumi Iida, Kazuki Iida, Takashi Miura, Susumu Saito
  • Journal Title: Journal of Synthetic Organic Chemistry, Japan Volume: 74 Issue: 11 Pages: 1078-1089
  • DOI: 10.5059/yukigoseikyokaishi.74.1078
  • NAID: 130005433322
  • ISSN: 0037-9980, 1883-6526
  • Peer Reviewed
• [Presentation] Catalytic hydrogen management：hydrogenation under dark and dehydrogenation under light (2018)
  • Author(s): Susumu Saito
  • Organizer: JSPS 3nd Core-to-core Seminar
  • Int'l Joint Research / Invited
• [Presentation] Catalytic hydrogen management of renewable feedstock：hydrogenation under dark and dehydrogenation under light (2018)
  • Author(s): Susumu Saito
  • Organizer: LIKAT seminar
  • Int'l Joint Research / Invited
• [Presentation] Catalytic hydrogen management of renewable feedstock：hydrogenation under dark and dehydrogenation under light (2018)
  • Author(s): Susumu Saito
  • Organizer: OIST Seminar
  • Int'l Joint Research / Invited
• [Presentation] Catalytic hydrogen management of renewable feedstock：hydrogenation under dark and dehydrogenation under light (2018)
  • Author(s): Susumu Saito
  • Organizer: AIST Seminar
  • Int'l Joint Research / Invited
• [Presentation] 精密水素移動場を用いるペプチド類の脱水的形成と変換 (2017)
  • Author(s): 斎藤進
  • Organizer: 真島新学術領域研究 第2回公開シンポジウム
  • Place of Presentation: 名古屋大学ES Hall，名古屋
  • Year and Date: 2017-01-25
  • Invited
• [Presentation] 触媒的水素マネージメント：熱と光で水素を操る化学変換 (2017)
  • Author(s): 斎藤進
  • Organizer: 非常勤講師特別講演会（群馬大学大学院理工学府学府セミナー）
  • Invited
• [Presentation] 遷移金属触媒を用いる再生可能資源の水素化と脱水素化 (2017)
  • Author(s): 斎藤進
  • Organizer: 統合物質創製化学機構 第3回国内シンポジウム
  • Invited
• [Presentation] 遷移金属触媒を用いる再生可能資源の精密化学変換への挑戦：「暗所」水素化から「光所」脱水素化へ…その後は？ (2017)
  • Author(s): 斎藤進
  • Organizer: 第50回有機金属若手の会夏の学校
  • Invited
• [Presentation] 分子触媒と固体触媒のクロスオーバー領域の精密化に基づく二酸化炭素の資源化法を目指して (2017)
  • Author(s): 斎藤進
  • Organizer: JACI / JST 交流セミナー
  • Invited
• [Presentation] 遷移金属錯体を用いるバイオマス関連カルボン酸の触媒的水素化 (2017)
  • Author(s): 斎藤進、鳴戸真之、二村聡太
  • Organizer: 第120回触媒討論会
• [Presentation] Catalytic hydrogenation of carboxylic acids using low- and high-valent transition metal complexes (2017)
  • Author(s): Susumu Saito
  • Organizer: Organometallic Chemistry, Gordon Research Conference (GRC)
  • Int'l Joint Research / Invited
• [Presentation] Catalytic Hydrogen Management: Hydrogenation under Dark and Dehydrogenation under Light (2017)
  • Author(s): Susumu Saito
  • Organizer: 1st International Symposium on Catalysis for Sustainable Chemical Synthesis
  • Int'l Joint Research / Invited
• [Presentation] 触媒的水素マネージメント：再生可能資源に豊富な官能基の還元と脱水 (2017)
  • Author(s): 斎藤進
  • Organizer: 三井化学（株）研究セミナー
  • Place of Presentation: 三井化学（株）袖ヶ浦センター，千葉
  • Invited
• [Presentation] 化学分野の将来展望 持続可能社会への化学の貢献を目指して (2017)
  • Author(s): 斎藤進
  • Organizer: ACT-C第1回社会的貢献推進会議
  • Place of Presentation: JST東京本部別館，市ヶ谷，東京
  • Invited
• [Presentation] 触媒的水素マネージメント：水素を操る化学変換 (2017)
  • Author(s): 斎藤進
  • Organizer: 豊田工業大学先進触媒開発研究センター第1回シンポジウム
  • Place of Presentation: 豊田工業大学，名古屋
  • Invited
• [Presentation] Metal carboxylylates as prototypical catalysts for self-induced hydrogenation of carboxylic acids (2016)
  • Author(s): Susumu Saito
  • Organizer: Catalysis & Fine Chemicals (C&FC)
  • Place of Presentation: Howard Civil Service International House, Taipei, Taiwan
  • Year and Date: 2016-11-10
  • Int'l Joint Research / Invited
• [Presentation] 金属カルボキシラートを触媒構造の原型とするカルボン酸の自己誘導型カルボン酸の水素化 (2016)
  • Author(s): 斎藤進，鳴戸真之，吉岡頌太，Ke Wen, Santosh Agrawal, 戸田勝章
  • Organizer: 第63回有機金属化学討論会
  • Place of Presentation: 早稲田大学，東京
  • Year and Date: 2016-09-14
  • Invited
• [Presentation] Catalytic hydrogen management: transformation of biomass-related inert compounds under light and dark (2016)
  • Author(s): Susumu Saito
  • Organizer: The 7th Annual Global Congress of Catalysis (GCC-2016)
  • Place of Presentation: Seoul, Korea
  • Year and Date: 2016-06-30
  • Int'l Joint Research / Invited
• [Presentation] 精密水素移動場を用いる修飾アミノ酸類の触媒的高効率脱水変換 (2016)
  • Author(s): 斎藤進
  • Organizer: 真島新学術領域研究 第１回全体会議
  • Place of Presentation: 大阪大学豊中キャンパス，大阪
  • Year and Date: 2016-05-13
  • Invited
• [Presentation] Catalytic hydrogen management using molecular- and photo-catalysis: transformation of biomass-related inert compounds (2016)
  • Author(s): Susumu Saito
  • Organizer: The 20th Joint Symposium of Core-to-Core Program on Elements Function for Transformative Catalysis and Materials
  • Place of Presentation: Queens University, Kingston, Canada
  • Int'l Joint Research / Invited
• [Presentation] 触媒的水素マネージメント：次世代物質合成を目指して (2016)
  • Author(s): 斎藤進
  • Organizer: 若手研究者のための有機合成セミナー，有機合成化学協会九州山口支部
  • Place of Presentation: 九州大学伊都キャンパス，福岡
  • Invited
• [Book] 理philosphia（フィロソフィア） (2017)
  • Author(s): 斎藤進
  • Total Pages: 1
  • Publisher: 名古屋大学理学部
• [Book] 化学工業＜特集＞戦略的触媒開発と応用（カルボン酸の水素化触媒の原型「ジホスフィン配位ルテニウムカルボキシラート」の発見と応用） (2016)
  • Author(s): 鳴戸真之，斎藤進
  • Total Pages: 8
  • Publisher: 化学工業社
• [Book] 名大トピックス (2016)
  • Author(s): 斎藤進
  • Total Pages: 2
  • Publisher: 名古屋大学
• [Remarks] Nagoya Researchers Break Down Plastic Waste
  • URL: http://en.nagoya-u.ac.jp/research/activities/news/2017/05/nagoya-university-researchers-break-down-plastic-waste.html
• [Remarks] Nagoya on its head for a sustainable future
  • URL: http://en.nagoya-u.ac.jp/research/activities/news/2017/06/nagoya-university-chemists-turn-metal-catalysis-on-its-head-for-a-sustainable-future.html