Palladium-catalyzed synthesis of fluorine-containing chiral allylic amines by a new stereocontrol

• Project/Area Number: 23550123
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Synthetic chemistry
• Research Institution: Nihon University (2012-2013); Tottori University (2011)
• Principal Investigator: KAWATSURA Motoi 日本大学, 文理学部, 教授 (50360243)
• Project Period (FY): 2011 – 2013
• Project Status: Completed (Fiscal Year 2013)
• Budget Amount: ¥5,200,000 (Direct Cost: ¥4,000,000、Indirect Cost: ¥1,200,000); Fiscal Year 2013: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000); Fiscal Year 2012: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000); Fiscal Year 2011: ¥2,340,000 (Direct Cost: ¥1,800,000、Indirect Cost: ¥540,000)
• Keywords: パラジウム / アリル位アミノ化 / 不斉合成 / フッ素 / アリルアミン / トリフルオロメチル基 / 動的速度論的光学分割 / パラジウム触媒 / エナンチオ選択性 / 銀塩 / 位置選択性 / アミノ化 / カチオン性

Research Abstract

The palladium-catalyzed regio- and enantioselective allylic amination of the trifluoromethyl group substituted racemic and unsymmetrical 1,3-disubstituted allylic esters has been accomplished. The enantioselective formation of the a-type allylic amines was attained by the dynamic kinetic asymmetric transformation (DYKAT).

Research Products

• [Journal Article] Enantioselective Allylic Amination of Trifluoromethyl Group Substituted Racemic and Unsymmetrical 1,3-Disubstituted Allylic Acetates by Palladium Catalysts (2014)
  • Author(s): Kawatsura, M.; Terasaki, S.; Minakawa, M.; Hirakawa, T.; Ikeda, K.; Itoh, T.
  • Journal Title: Org. Lett. Volume: 16 Issue: 9 Pages: 2443-2445
  • DOI: 10.1021/ol5008229
  • Peer Reviewed
• [Journal Article] Palladium catalyzed Double Substitution of 3-Aryl-2-fluoroallyl Acetates with Phenols via C-F Bond Activation (2014)
  • Author(s): Nomada, E.; Watanabe, H.; Yamamoto, M.; Udagawa, T.; Minakawa, M.; Zhou, B.; Kobayashi, A.; Kawatsura, M.
  • Journal Title: Synlett Volume: (in press)
  • Peer Reviewed
• [Journal Article] Ruthenium-Catalyzed Regio- and Enantioselective Allylic Amination of Racemic 1-Arylally Esters (2014)
  • Author(s): Kawatsura, M.; Uchida, K.; Terasaki, S.; Tsuji, H.; Minakawa, M.; Itoh, T.
  • Journal Title: Organic Letters Volume: 16 Issue: 5 Pages: 1470-1473
  • DOI: 10.1021/ol5002768
  • Peer Reviewed
• [Journal Article] Palladium-Catalyzed Double Alkyaltion of 3-Aryl-2-fluoroallyl Esters through the Carbon-Fluorine Bond Cleavage (2014)
  • Author(s): Yamamoto, M.; Hayashi, S.; Isa, K.; Kawatsura, M.
  • Journal Title: Org. Lett. Volume: 16 Issue: 3 Pages: 700-703
  • DOI: 10.1021/ol500121z
  • Peer Reviewed
• [Journal Article] Enantioselective Allylic Amination of Trifluoromethyl Group Substituted Racemic and Unsymmetrical 1,3-Disubstituted Allylic Acetates by Palladium Catalysts (2014)
  • Author(s): Kawatsura, M.; Terasaki, S.; Minakawa, M.; Hirakawa, T.; Ikeda, K.; Itoh, T.
  • Journal Title: Org. Lett Volume: 16
  • Peer Reviewed
• [Journal Article] Palladium-catalyzed Double Substitution of 3-Aryl-2-fluoroallyl Acetates with Phenols via C-F Bond Activation (2014)
  • Author(s): Nomada, E.; Watanabe, H.; Yamamoto, M.; Udagawa, T.; Minakawa, M.; Zhou, B.; Kobayashi, A.; Kawatsura, M.
  • Journal Title: Synlett Volume: 25
  • Peer Reviewed
• [Journal Article] A Chronicle Review : Regioselective Synthesis of Trifluoromethyl Group Containing Allylic Amines using Palladium-catalyzed Allylic Amination Pathway (2013)
  • Author(s): Hirakawa, T.; Kawatsura, M. ; Itoh, T.
  • Journal Title: J. Fluorine Chem. Volume: 152 Pages: 62-69
  • DOI: 10.1016/j.jfluchem.2013.03.008
  • Peer Reviewed
• [Journal Article] Regioselective synthesis of trifluoromethyl group containing allylic amines by palladium-catalyzed allylic amination and sequential isomerization (2011)
  • Author(s): Hirakawa, T.; Ikeda, K.; Ikeda, D.; Tanaka, T.; Ogasa, H.; Kawatsura, M.; Itoh, T.
  • Journal Title: Tetrahedron Volume: 67 Issue: 43 Pages: 8238-8247
  • DOI: 10.1016/j.tet.2011.08.093
  • Peer Reviewed
• [Journal Article] Regioselective synthesis of trifluoromethyl group containing allylic amines by palladium-catalyzed allylic amination and sequential isomerization (2011)
  • Author(s): Hirakawa, T.; Ikeda, K,; Ikeda, D.; Tanaka, T.; Ogasa, H.; Kawatsura, M.; Itoh, T.
  • Journal Title: Tetrahedron Volume: 67 Issue: 40 Pages: 6747-6757
  • DOI: 10.1016/j.tet.2011.08.016
  • Peer Reviewed
• [Journal Article] Palladium-catalyzed Regio- and Diastereoselective Allylic Alkylation in Ionic Liquids (2011)
  • Author(s): Kawatsura, M.; Nobuto, H.; Hayashi, S.; Hirakawa, T.; Ikeda, D.; Itoh, T.
  • Journal Title: Chem. Lett. Volume: 40 Issue: 9 Pages: 953-955
  • DOI: 10.1246/cl.2011.953
  • NAID: 10029521942
  • Peer Reviewed
• [Journal Article] Retention of Regiochemistry and Chirality in the Ruthenium Catalyzed Allylic Alkylation of Disubstituted Allylic Esters (2011)
  • Author(s): Kawatsura, M.; Sato, M.; Tsuji, H,; Ata, F.; Itoh, T.
  • Journal Title: J.Org.Chem. Volume: 76 Issue: 13 Pages: 5485-5488
  • DOI: 10.1021/jo2007169
  • Peer Reviewed
• [Presentation] 含フッ素アリルアセテートのトリフルオロメチル基構築を伴うパラジウム触媒アミノ化反応 (2014)
  • Author(s): 伊佐一希・皆川真規・川面基
  • Organizer: 日本化学会第94春季年会
  • Place of Presentation: 名古屋(2B1-47)
  • Year and Date: 2014-03-28
• [Presentation] 2-フルオロアリルアセテートのPd触媒ダブルエーテル化反応 (2014)
  • Author(s): 渡邊弘高・野間田英人・山本光昭・皆川真規・川面基
  • Organizer: 日本化学会第94春季年会
  • Place of Presentation: 名古屋(2B4-46)
  • Year and Date: 2014-03-28
• [Presentation] 鉄触媒を用いたトリフルオロメチル基を有する非対称内部アルキンと1,6-ジインによる[2+2+2]環化付加反応 (2014)
  • Author(s): 石川知紀・浪岡純也・広岡宗一郎・皆川真規・川面基
  • Organizer: 日本化学会第94春季年会
  • Place of Presentation: 名古屋(2B1-50)
  • Year and Date: 2014-03-28
• [Presentation] ルテニウム触媒を用いたラセミ体アリルエステルのエナンチオ選択的アリル位アミノ化反応 (2014)
  • Author(s): 寺崎奨,内田健太,皆川真規,川面基
  • Organizer: 日本化学会第94春季年会
  • Place of Presentation: 名古屋(1B3-17)
  • Year and Date: 2014-03-27
• [Presentation] 2-Fluoro-3-arylallylacetatesのPd触媒ヒドロアルキル化反応 (2012)
  • Author(s): 九鬼しほ里,川面基,伊藤敏幸
  • Organizer: 第2回CSJ化学フェスタ2012
  • Place of Presentation: 東京
  • Year and Date: 2012-10-16
• [Presentation] ルテニウム触媒を用いた不斉アリル位アミノ化反応 (2012)
  • Author(s): 内田健太,川面基,伊藤敏幸
  • Organizer: 第2回CSJ化学フェスタ2012
  • Place of Presentation: 東京
  • Year and Date: 2012-10-16
• [Presentation] 含フッ素モノ置換アリルアセテートのPd触媒ダブルアルキル化反応 (2011)
  • Author(s): 山本光昭,林駿輔,川面基,伊藤敏幸
  • Organizer: 第58回有機金属化学討論会
  • Place of Presentation: 名古屋(P3A-06)
  • Year and Date: 2011-09-09
• [Presentation] Ir触媒アリル位アルキル化反応におけるアズラクトンおよびオキサゾリノン誘導体の立体選択的合成 (2011)
  • Author(s): 辻裕章,内田健太,川面基,伊藤敏幸
  • Organizer: 第58回有機金属化学討論会
  • Place of Presentation: 名古屋(P2C-31)
  • Year and Date: 2011-09-08
• [Presentation] Iridium-catalyzed Allylic Alkylation of Monosubstituted Allylic Acetates with Azlactone, and Separation of Diastereoisomers by Sequential Aza-Cope Rearrangement (2011)
  • Author(s): Tsuji, H.; Uchida, K.; Kawatsura, M.; Itoh, T.
  • Organizer: 16th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS 16)
  • Place of Presentation: Shanghai, China
  • Year and Date: 2011-07-26
• [Presentation] Palladium-catalyzed Double Substitution of Fluorine-contained Monosubstituted Allylic Esters with Malonate Nucleophile (2011)
  • Author(s): Yamamoto, M.; Hayashi, S.; Kuki, S.; Kawatsura, M.; Itoh, T.
  • Organizer: 16th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS 16)
  • Place of Presentation: Shanghai, China
  • Year and Date: 2011-07-26
• [Remarks]
  • URL: http://www.chs.nihon-u.ac.jp/chem_dpt/lab/kawatsura/Kawatsura_group/TOP.html