Transfer Hydration and Dehydration

• Project/Area Number: 17K05859
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Synthetic chemistry
• Research Institution: Nagoya University
• Principal Investigator: Naka Hiroshi 名古屋大学, 物質科学国際研究センター, 助教 (70431517)
• Project Period (FY): 2017-04-01 – 2020-03-31
• Project Status: Completed (Fiscal Year 2019)
• Budget Amount: ¥4,810,000 (Direct Cost: ¥3,700,000、Indirect Cost: ¥1,110,000); Fiscal Year 2019: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000); Fiscal Year 2018: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000); Fiscal Year 2017: ¥2,600,000 (Direct Cost: ¥2,000,000、Indirect Cost: ¥600,000)
• Keywords: ニトリル / アミド / 水和 / 脱水 / パラジウム / 水移動型反応 / シアノヒドリン / 水和反応 / ポリアクリロニトリル / 共重合体 / パラジウム触媒 / グルタロニトリル / ヒドロキシアミド / 触媒 / 水 / 脱水反応 / 触媒反応 / 合成化学 / 触媒・化学プロセス / 有機化学

Outline of Final Research Achievements

Interconversion reaction between nitriles and primary amides is an important process in organic synthesis. This report describes the development of palladium-catalyzed transfer hydration of nitriles using carboxamides as a water donor. Successful examples of nitriles include ketone-derived cyanohydrins and glutaronitriles. Also, palladium-catalyzed transfer dehydration of amides to nitriles was demonstrated using electron-deficient nitriles as a water acceptor.

Academic Significance and Societal Importance of the Research Achievements

水の分子間移動を触媒的に制御する「水移動型反応の化学」の提案は，有機化学に新しい考え方をもたらすものと位置付けられる．また，本研究を通して複雑なニトリルとアミドの効率的な合成法を提供することができた．本研究で開発した合成法はすでに物質合成の場面で利用されつつあり，今後も合成化学の進歩に対する貢献が期待できる．以上を通した医薬化学，物質科学，生命科学などの学術領域や精密合成化学産業に対する波及効果が期待できる．

Research Products

• [Journal Article] Recent Advances in Transfer Hydration of Nitriles with Amides or Aldoximes (2020)
  • Author(s): Naka Hiroshi, Naraoka Asuka
  • Journal Title: Tetrahedron Letters Volume: 61 Issue: 10 Pages: 151557-151557
  • DOI: 10.1016/j.tetlet.2019.151557
  • NAID: 120006869624
  • Peer Reviewed
• [Journal Article] Transfer Hydration of Dinitriles to Dicarboxamides (2019)
  • Author(s): Naraoka Asuka, Naka Hiroshi
  • Journal Title: Synlett Volume: 30 Issue: 17 Pages: 1977-1980
  • DOI: 10.1055/s-0039-1690026
  • NAID: 120006727121
  • Peer Reviewed
• [Journal Article] Acceptor-Controlled Transfer Dehydration of Amides to Nitriles (2019)
  • Author(s): Okabe Hiroyuki、Naraoka Asuka、Isogawa Takahiro、Oishi Shunsuke、Naka Hiroshi
  • Journal Title: Organic Letters Volume: 21 Issue: 12 Pages: 4767-4770
  • DOI: 10.1021/acs.orglett.9b01657
  • Peer Reviewed
• [Journal Article] Pd‐Catalyzed β‐Selective C-H Arylation of Thiophenes with Triarylantimony Difluorides (2019)
  • Author(s): Kitamura Yuki、Murata Yuki、Oguri Ayaka、Matsumura Mio、Kakusawa Naoki、Naka Hiroshi、Yasuike Shuji
  • Journal Title: Asian Journal of Organic Chemistry Volume: 8 Issue: 1 Pages: 138-143
  • DOI: 10.1002/ajoc.201800654
  • NAID: 120006623816
• [Journal Article] Catalytic Transfer Hydration of Cyanohydrins to α-Hydroxyamides (2018)
  • Author(s): Kanda Tomoya、Naraoka Asuka、Naka Hiroshi
  • Journal Title: Journal of the American Chemical Society Volume: 141 Issue: 2 Pages: 825-830
  • DOI: 10.1021/jacs.8b12877
  • NAID: 120006623815
  • Peer Reviewed
• [Presentation] Transfer Hydration of Dinitriles to Diamides (2020)
  • Author(s): Asuka Naraoka, Hiroshi Naka
  • Organizer: The 3rd IRCCS - The 2nd Reaction Infography Joint International Symposium, Jan 31-Feb 1, 2020, Nagoya University, Nagoya (poster).
  • Int'l Joint Research
• [Presentation] Synthesis of α-Amino Amides by Transfer Hydration of Nitriles (2020)
  • Author(s): Tomoyo Tamura, Taimeng Liang, Ryoji Noyori, Hiroshi Naka
  • Organizer: The 3rd IRCCS - The 2nd Reaction Infography Joint International Symposium, Jan 31-Feb 1, 2020, Nagoya University, Nagoya (poster).
  • Int'l Joint Research
• [Presentation] 水移動型反応によるアクロリニトリル-アクリルアミド共重合体の精密合成 (2020)
  • Author(s): 奈良岡 あすか，有津 拓，内山 峰人，浅井 駿輝，野依 良治，上垣外 正己，中 寛史
  • Organizer: 日本化学会第100春季年会，2020年3月22-25日，東京理科大学，千葉（ポスター）．
• [Presentation] Palladium-Catalyzed Transfer Hydration of Dinitriles to Diamides (2020)
  • Author(s): Asuka Naraoka, Ryoji Noyori, Hiroshi Naka
  • Organizer: 日本化学会第100春季年会，2020年3月22-25日，東京理科大学，千葉（口頭）．
• [Presentation] Transfer Hydration of α-Amino Nitriles for Amino Acid Synthesis (2020)
  • Author(s): Tomoyo Tamura, Taimeng Liang, Ryoji Noyori, Hiroshi Naka
  • Organizer: 日本化学会第100春季年会，2020年3月22-25日，東京理科大学，千葉（ポスター）．
• [Presentation] (Photo)catalytic Conversion of Water and Alcohols for Selective Chemical Synthesis (2019)
  • Author(s): Hiroshi Naka
  • Organizer: Department Seminar, Nov 19, 2019, Nanjing University of Science and Technology, China (invited).
  • Int'l Joint Research / Invited
• [Presentation] Catatlytic Transfer Hydration of Cyanohydrins to alpha-Hydroxyamides (2019)
  • Author(s): Tomoya Kanda, Asuka Naraoka, Hiroshi Naka
  • Organizer: The 4th International Symposium on Process Chemistry, Jul 24-26, 2019, Kyoto International Conference Center, Kyoto (oral and poster)
  • Int'l Joint Research
• [Presentation] Acceptor-controlled Transfer Dehydration of Amides to Nitriles (2019)
  • Author(s): Asuka Naraoka, Hiroyuki, Okabe, Takahiro Isogawa, Shunsuke Oishi, Hiroshi Naka
  • Organizer: The 4th International Symposium on Process Chemistry, Jul 24-26, 2019, Kyoto International Conference Center, Kyoto (poster).
  • Int'l Joint Research
• [Presentation] Synthesis of α-Amino Amides by Transfer Hydration of Nitriles (2019)
  • Author(s): Tomoyo Tamura, Taimeng Liang, Ryoji Noyori, Hiroshi Naka
  • Organizer: 統合物質創製化学研究推進機構 第5回国内シンポジウム 物質創製化学のフロンティア，2019年11月18-19日，北海道大学，北海道（ポスター）．
• [Presentation] 人の生き方を変える化学 (2019)
  • Author(s): 中 寛史
  • Organizer: 名古屋市立向陽高校模擬授業，2019年10月31日，向陽高校，名古屋（招待）．
  • Invited
• [Presentation] 水とアルコールを使った(光)触媒的合成化学 (2019)
  • Author(s): 中 寛史
  • Organizer: 京大人環物質機能相関論セミナー，2019年10月16日，京都大学，京都（招待）．
  • Invited
• [Presentation] 触媒的水移動型水和反応による α-アミノアミドの迅速合成 (2019)
  • Author(s): 田村 知世，野依 良治，中 寛史
  • Organizer: 第 36 回有機合成化学セミナー，2019年9月17-19日，長良川国際会議場，岐阜（ポスター）．
• [Presentation] 水移動型水和反応によるジアミド合成 (2019)
  • Author(s): 中 寛史
  • Organizer: AIKOC-3，2019年8月31日，大阪大学，大阪（ポスター）.
• [Presentation] 新しい化学反応を使って未知のアミノ酸をつくる！ (2019)
  • Author(s): 田村 知世，野依 良治，中 寛史
  • Organizer: 名古屋大学若手女性研究者サイエンスフォーラム，2019年7月17日，名古屋大学，名古屋（ポスター）．
• [Presentation] 触媒的水移動型水和反応による α-アミノアミドの迅速合成 (2019)
  • Author(s): 田村 知世，野依 良治，中 寛史
  • Organizer: 日本薬学会第139年会
• [Presentation] ニトリルの触媒的水移動型水和反応の開発 (2019)
  • Author(s): 奈良岡 あすか, 神田 智哉, 田村 知世，野依 良治，中 寛史
  • Organizer: 日本薬学会第139年会
• [Presentation] パラジウム触媒を用いた水移動型水和反応の反応機構 (2019)
  • Author(s): 奈良岡 あすか, 神田 智哉, 中 寛史
  • Organizer: 日本化学会第99春季年会
• [Presentation] Transfer (De)hydration Catalysis (2019)
  • Author(s): Hiroshi Naka
  • Organizer: Core-to-Core Symposium “Elements Function for Transformative Catalysis and Materials”
  • Int'l Joint Research / Invited
• [Presentation] (Photo)catalytic Conversion of Water and Alcohols for Selective Chemical Synthesis (2019)
  • Author(s): Hiroshi Naka
  • Organizer: Chemistry Department Seminar, Jan 31, 2019, Dalhousie University, Canada
  • Int'l Joint Research / Invited
• [Presentation] (Photo)catalytic Conversion of Water and Alcohols for Selective Chemical Synthesis (2019)
  • Author(s): Hiroshi Naka
  • Organizer: McGill Chemical Society Seminar, Jan 30, 2019, McGill University, Canada
  • Int'l Joint Research / Invited
• [Presentation] (Photo)catalytic Conversion of Water and Alcohols for Selective Chemical Synthesis (2019)
  • Author(s): Hiroshi Naka
  • Organizer: Chemistry Department Seminar, Jan 28, 2019, Queen’s University, Canada
  • Int'l Joint Research / Invited
• [Presentation] (Photo)catalytic Conversion of Water and Alcohols for Selective Chemical Synthesis (2019)
  • Author(s): Hiroshi Naka
  • Organizer: The 2nd International Symposium of IRCCS, Jan 25－26, 2019, Kyoto University, Kyoto
  • Int'l Joint Research / Invited
• [Presentation] (Photo)catalytic Conversion of Water and Alcohols for Selective Chemical Synthesis (2019)
  • Author(s): Hiroshi Naka
  • Organizer: Special Department Seminar, Jan 25, 2019, University of Ottawa, Canada
  • Int'l Joint Research / Invited
• [Presentation] (Photo)catalytic Conversion of Water and Alcohols for Selective Chemical Synthesis (2019)
  • Author(s): Hiroshi Naka
  • Organizer: Special Chemistry Seminar, Jan 24, 2019, University of Toronto, Canada
  • Int'l Joint Research / Invited
• [Presentation] (Photo)catalytic Conversion of Water and Alcohols for Selective Chemical Synthesis (2019)
  • Author(s): Hiroshi Naka
  • Organizer: Department Seminar, Jan 23, 2019, University of Alberta, Canada
  • Int'l Joint Research / Invited
• [Presentation] (Photo)catalytic Conversion of Water and Alcohols for Selective Chemical Synthesis (2019)
  • Author(s): Hiroshi Naka
  • Organizer: Organic Seminar, Jan 21, 2019, University of British Colombia, Canada
  • Int'l Joint Research / Invited
• [Presentation] Palladium-Catalyzed Transfer Hydration of Cyanohydrins (2019)
  • Author(s): Asuka Naraoka, Tomoya Kanda, Hiroshi Naka
  • Organizer: The 2nd International Symposium of IRCCS
  • Int'l Joint Research
• [Presentation] 水とアルコールを使った(光)触媒的合成化学 (2018)
  • Author(s): 中 寛史
  • Organizer: 京大人環 分子環境相関論ウインターセミナー2018
• [Presentation] Transfer Hydration of Cyanohydrins (2018)
  • Author(s): Hiroshi Naka, Tomoya Kanda, Asuka Naraoka, Ryoji Noyori
  • Organizer: The 14th International Kyoto Conference on New Aspects of Organic Chemistry (IKCOC-14),
• [Presentation] 水の分子変換化学 (2018)
  • Author(s): 中 寛史
  • Organizer: 講演会~分子変換の深化~
  • Invited
• [Presentation] シアノヒドリンの水移動型水和反応によるa-ヒドロキシアミドの合成 (2018)
  • Author(s): 神田 智哉，野依 良治，中 寛史
  • Organizer: 日本薬学会第138年会
• [Presentation] シアノヒドリンの水移動型水和反応 (2018)
  • Author(s): 神田 智哉，野依 良治，中 寛史
  • Organizer: 日本化学会第98春季年会
• [Presentation] Transfer Dehydration of Primary Amides Using Electron-Deficient Nitriles (2018)
  • Author(s): Hiroyuki Okabe, Takahiro Isogawa, Asuka Naraoka, Ryoji Noyori, Hiroshi Naka
  • Organizer: 日本化学会第98春季年会
• [Presentation] 電子不足ニトリルを用いた一級カルボン酸アミドの水移動型脱水反応 (2018)
  • Author(s): 岡部 弘幸，五十川 貴裕，奈良岡 あすか，野依 良治，中 寛史
  • Organizer: 日本化学会第98春季年会
• [Presentation] 水で有機物質をつくる (2017)
  • Author(s): 中 寛史
  • Organizer: JPIJS 関西地区討論会
  • Invited
• [Presentation] パラジウム触媒と電子不足ニトリルを用いた一級アミドの水中脱水反応 (2017)
  • Author(s): 岡部 弘幸，五十川 貴裕，野依 良治，中 寛史
  • Organizer: 第34回有機合成化学セミナー
• [Presentation] 水で有機物質をつくる (2017)
  • Author(s): 中 寛史
  • Organizer: バイオ元素戦略懇談会
• [Remarks] Naka Reserach Group
  • URL: http://noy.chem.nagoya-u.ac.jp/H_Naka-J/
• [Remarks] 研究グループ
  • URL: http://noy.chem.nagoya-u.ac.jp/H_Naka-J/
• [Remarks] 野依特別研究室
  • URL: http://noy.chem.nagoya-u.ac.jp/noy_j/
• [Remarks] 化学科での論文紹介記事
  • URL: http://www3.chem.nagoya-u.ac.jp/wordpress/?p=11732