Development of cascade cyclization reaction via the direct activation of propargylalcohols

• Project/Area Number: 26460009
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Chemical pharmacy
• Research Institution: Tokushima Bunri University (2015-2016); The University of Tokushima (2014)
• Principal Investigator: YOSHIDA MASAHIRO 徳島文理大学, 薬学部, 教授 (10344681)
• Project Period (FY): 2014-04-01 – 2017-03-31
• Project Status: Completed (Fiscal Year 2016)
• Budget Amount: ¥5,070,000 (Direct Cost: ¥3,900,000、Indirect Cost: ¥1,170,000); Fiscal Year 2016: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000); Fiscal Year 2015: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000); Fiscal Year 2014: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
• Keywords: プロパルギルアルコール / 活性化 / パラジウム / ルイス酸 / 求核剤 / 連続反応 / 連続的環化反応

Outline of Final Research Achievements

Propargylic compounds having an elimination group at the propargylic position are known as useful substrates in the palladium-catalyzed reactions. The reaction often employs activated propargylic alcohol derivatives such as propargylic esters, carbonates and halides, and no examples have been reported about the palladium-catalyzed reactions of underivatized propargylic alcohols with soft nucleophiles. The author developed palladium and boric acid-catalyzed cyclization of underivatized 1,3-diaryl propargylic alcohols with 1,3-cyclohexanediones. Boric acid plays a role for the efficient activation of the propargylic alcohols. Various substituted tetrahydrobenzofuranones were obtained in moderate to good yields. Reactions using 4-hydroxy-2-pyrones as the nucleophile also proceeded to afford the substituted dihydrofuropyranones.

Research Products

• [Journal Article] Syntheses of 2-Vinyl-2,3-dihydropyrroles and 3-Methylene-1,2,3,4-tetrahydropyridines by Palladium-Catalyzed Cyclization of N-Tosyl Imines with Allylic Diesters (2017)
  • Author(s): Masahiro Yoshida, Kouki Kinoshita, and Kosuke Namba
  • Journal Title: Heterocycles Volume: 95 Issue: 1 Pages: 410-421
  • DOI: 10.3987/com-16-s(s)33
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Aerobic C-H Oxidation of Arenes Using a Recyclable, Heterogeneous Rhodium Catalyst (2017)
  • Author(s): Kenji Matsumoto, Shohei Tachikawa, Noriko Hashimoto, Rina Nakano, Masahiro Yoshida, and Mitsuru Shindo
  • Journal Title: The Journal of Organic Chemistry Volume: 82 Issue: 8 Pages: 4305-4316
  • DOI: 10.1021/acs.joc.7b00300
  • Peer Reviewed
• [Journal Article] Selective Synthesis of Cyclic Compounds by Palladium-Catalyzed Cyclization of Propargylic Esters with Nucleophiles (2017)
  • Author(s): 吉田 昌裕
  • Journal Title: Journal of Synthetic Organic Chemistry, Japan Volume: 75 Issue: 1 Pages: 38-48
  • DOI: 10.5059/yukigoseikyokaishi.75.38
  • NAID: 130005296270
  • ISSN: 0037-9980, 1883-6526
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Direct cyclization of 1,3-diaryl propargylic alcohols with dicarbonyl compounds by palladium-boric acid dual-catalyst system. (2016)
  • Author(s): Masahiro Yoshida, Shoko Ohno, Sayaka Eguchi, Tomotaka Mizuguchi, Kosuke Namba
  • Journal Title: Tetrahedron Volume: 27 Issue: 36 Pages: 2591-2596
  • DOI: 10.1016/j.tet.2016.07.055
  • Peer Reviewed
• [Journal Article] Synthesis of functionalized 2,3-dihydropyrroles by oxidative radical cyclization of N-sulfonyl β-enamino esters with alkenes. (2016)
  • Author(s): Masahiro Yoshida, Asuka Kobayashi, Atsushi Nakayama, Kosuke Namba
  • Journal Title: Tetrahedron Volume: 72 Issue: 20 Pages: 2544-2551
  • DOI: 10.1016/j.tet.2016.03.055
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Synthesis of 2,3-Dihydro-4H-furo[3,2-c]chromen-4-one Derivatives by Oxidative Radical Cyclization of 4-Hydroxy-2H-chromen-2-one with Alkenes. (2016)
  • Author(s): Masahiro Yoshida, Asuka Kobayashi, Kosuke Namba
  • Journal Title: Heterocycles Volume: 93 Issue: 2 Pages: 737-737
  • DOI: 10.3987/com-15-s(t)27
  • Peer Reviewed
• [Journal Article] Rhodium-Catalyzed Aerobic Oxidative Dehydrogenative Cross-Coupling: Nonsymmetrical Biaryl Amines. (2016)
  • Author(s): Kenji Matsumoto, Masahiro Yoshida, Mitsuru Shindo
  • Journal Title: Angewandte Chemie, International Edition Volume: 55 Issue: 17 Pages: 5272-5276
  • DOI: 10.1002/anie.201600400
  • Peer Reviewed
• [Journal Article] Total Synthesis of Palau’amine (2015)
  • Author(s): K. Namba, K. Takeuchi, Y. Kaihara, M. Oda, A. Nakayama, A. Nakayama, M. Yoshida, and K. Tanino
  • Journal Title: Nature Communications Volume: 6 Issue: 1 Pages: 8731-8731
  • DOI: 10.1038/ncomms9731
  • NAID: 120006999407
  • Peer Reviewed / Open Access / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Synthesis of functionalized 2-vinyl-2,3-dihydropyrroles and 3-methylene-1,2,3,4-tetrahydropyridines by palladium-catalyzed cyclization of ß-enaminocarbonyl compounds with allylic bisacetates (2014)
  • Author(s): Masahiro Yoshida, Kouki Kinoshita and Kosuke Namba
  • Journal Title: Organic & Biomolecular Chemistry Volume: 12 Issue: 15 Pages: 2394-2403
  • DOI: 10.1039/c3ob42510j
  • Peer Reviewed
• [Journal Article] Total synthesis of (-)-HM-3 and (-)-HM-4 utilizing a palladium-catalyzed addition of an arylboronic acid to an allenic alcohol-Eschenmoser-Claisen rearrangement (2014)
  • Author(s): Masahiro Yoshida, Tomoyo Kasai, Tomotaka Mizuguti and Kosuke Namba
  • Journal Title: Synlett Volume: 25 Issue: 08 Pages: 1160-1162
  • DOI: 10.1055/s-0033-1341059
  • Peer Reviewed
• [Presentation] N-アリールメチルプロパルギルアジリジンの開環・環化反応を鍵反応としたラスビンIIの全合成研究 (2017)
  • Author(s): 須藤彰太、水口智貴、廣兼司、松本健司、難波康祐、吉田昌裕
  • Organizer: 日本薬学会137年会
  • Place of Presentation: 仙台
• [Presentation] パラジウム触媒を用いた2－メチレン－1,3-プロパンジオールとβ－ジカルボニル化合物の環化反応 (2017)
  • Author(s): 江口彩香、廣兼司、松本健司、吉田昌裕
  • Organizer: 日本薬学会137年会
  • Place of Presentation: 仙台
• [Presentation] パラジウム触媒を用いたアリルジエステルと4-ヒドロキシ-2-ピロンの環化反応によるジヒドロピラノピラン骨格の構築 (2017)
  • Author(s): 古田絵莉香、向井達哉、廣兼司、松本健司、吉田昌裕
  • Organizer: 日本薬学会137年会
  • Place of Presentation: 仙台
• [Presentation] 含窒素芳香族化合物の触媒的ビアリールカップリング反応の開発 (2017)
  • Author(s): 松本健司、興梠彰太、酒井健太郎、新藤充、吉田昌裕
  • Organizer: 日本薬学会137年会
  • Place of Presentation: 仙台
• [Presentation] アルキニルアジリジンの 1,5-水素移動を鍵とする置換ピロリンの立体選択的合成 (2016)
  • Author(s): 水口智貴、和田文恵、中山淳、難波康祐、吉田昌裕
  • Organizer: 日本薬学会136年会
  • Place of Presentation: パシフィコ横浜（神奈川県横浜市）
  • Year and Date: 2016-03-27
• [Presentation] アリールプロパルギルエーテルの不斉 [2+2] 環化付加反応の開発 (2016)
  • Author(s): 森岡亨平、加藤光貴、水口智貴、中山淳、難波康祐、吉田昌裕
  • Organizer: 日本薬学会136年会
  • Place of Presentation: パシフィコ横浜（神奈川県横浜市）
  • Year and Date: 2016-03-27
• [Presentation] パラジウム触媒を用いたプロパルギルアルコールとβ-ジカルボニル化合物の環化反応 (2016)
  • Author(s): 江口彩香、大野祥子、水口智貴、難波康祐、吉田昌裕
  • Organizer: 日本薬学会136年会
  • Place of Presentation: パシフィコ横浜（神奈川県横浜市）
  • Year and Date: 2016-03-27
• [Presentation] パラジウム触媒を用いたアリルジエステルと4-ヒドロキシ-2-ピロンの連続的環化反応 (2016)
  • Author(s): 向井達哉、古田絵莉香、廣兼司、松本健司、吉田昌裕
  • Organizer: 第55回日本薬学会中四国支部学術大会
  • Place of Presentation: 岡山
• [Presentation] アルキニルアジリジンの 1,5-水素移動を鍵とする置換ピリジン及びピペリジンの選択的合成 (2015)
  • Author(s): 水口智貴、中山淳、難波康祐、吉田昌裕
  • Organizer: 第45回複素環化学討論会
  • Place of Presentation: 早稲田大学国際会議場（東京都新宿区）
  • Year and Date: 2015-11-19
• [Presentation] パラジウム触媒を用いたプロパルギルアルコールと環状ジケトンの連続的環化反応 (2014)
  • Author(s): 大野祥子、吉田昌裕、難波康祐
  • Organizer: 第53回日本薬学会・日本薬剤師会・日本病院薬剤師会 中国四国支部学術大会
  • Place of Presentation: 広島国際会議場（広島県広島市）
  • Year and Date: 2014-11-08 – 2014-11-09
• [Presentation] Palladium-Catalyzed Cyclization of Propargylic Esters with Nucleophiles (2014)
  • Author(s): Masahiro Yoshida
  • Organizer: 3rd International Conference on Organic Chemistry
  • Place of Presentation: トビリシ（グルジア）
  • Year and Date: 2014-09-25 – 2014-09-28
  • Invited