Development of novel synthetic reactions based on release of strain energy in small ring system and its application to total syntheses of natural products

2013 Fiscal Year Final Research Report

• Project/Area Number: 22590023
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Chemical pharmacy
• Research Institution: Kyoto Pharmaceutical University
• Principal Investigator: YAMASHITA Masayuki 京都薬科大学, 薬学部, 教授 (20239982)
• Co-Investigator(Kenkyū-buntansha): KOJIMA Naoto 京都薬科大学, 薬学部, 講師 (90420413)
• Project Period (FY): 2010-04-01 – 2013-03-31
• Keywords: 環歪み / シクロプロパン / 骨格変換反応 / 2-オキソ-2H-ピラン-3-カルボン酸 / ビシクロ[3.1.0]ヘキサン-3-カルボン酸 / ジヒドロ-3aH-シクロペンタ[b]フラン / アダンクチンＢ / イリド

Research Abstract

A small ring system such as cyclopropane ring and cyclobutane ring is one of the important functional groups to easily ring-open due to their ring strain release in organic synthetic chemistry.
The reaction of alfa-pyrone derivatives which have an electron-withdrawing group at the 3-position with dimethylsulfoxonium methylide was examined. Bicycle[3.1.0]hexane derivatives and cyclopentadihydrofuran derivatives were selectively obtained on the basis of difference between substituent groups on the 5-position of alfa-pyrone. Furthermore, a natural product, adunctin B, was synthesized via a key reaction of coumarin which has an electron-withdrawing group at the 3-position with dimethylsulfoxonium methylide.

Research Products

• [Journal Article] Skeleton transformation ofα-pyrone induced by 5-aryl substituent into ring-fused dihydrofuran (2014)
  • Author(s): Takuya Miura, Saki Fujioka, Hiroki Iwasaki, Minoru Ozeki, Naoto Kojima, Masayuki Yamashita
  • Journal Title: Tetrahedron Lett. Volume: 55 Pages: 1536-1539
  • DOI: 10.1016/j.tetlet.2014.01.057
  • Peer Reviewed
• [Journal Article] Synthesis of 6-subtituted 3-(Alkoxycarbonyl)-5-aryl-α-pyrones (2014)
  • Author(s): Takuya Miura, Saki Fujioka, Naoto Takemura, Hiroki Iwasaki, Minoru Ozeki, Naoto Kojima, Masayuki Yamashita
  • Journal Title: Synthesis Volume: 46 Pages: 496-502
  • DOI: 10.1055/s-0033-1338575
  • Peer Reviewed
• [Journal Article] Synthesis of (±)-8-deisopropyladunctin B (2012)
  • Author(s): Sayo Nomura, Kenji Arimitsu, Satoshi Yamaguchi, Yuya Kosuga, Yuko Kakimoto, Takanori Komai, Kazumasa Hasegawa, Akira Nakanishi, Tamami Miyoshi, Hiroki Iwasaki, Minoru Ozeki, Ikuo Kawasaki, Ai Kurume, Shunsaku Ohta, Masayuki Yamashita
  • Journal Title: Chem. Pharm. Bull. Volume: 60 Pages: 94-103
  • DOI: 10.1248/cpb.60.94
  • Peer Reviewed
• [Journal Article] Novel skeleton transformation reaction ofα-pyrone derivatives to spirobicyclo[3.1.0]hexane derivatives using dimethylsulfoxonium methylide (2012)
  • Author(s): Takuya Miura, Navnath Dnyanoba Yadav, Hiroki Iwasaki, Minoru Ozeki, Naoto Kojima, Masayuki Yamashita
  • Journal Title: Org. Lett. Volume: 14 Pages: 6048-6051
  • DOI: 10.1021/ol302942m
  • Peer Reviewed
• [Journal Article] First total synthesis of (±)-adunctin B (2011)
  • Author(s): Kenji Arimitsu, Sayo Nomura, Hiroki Iwasaki, Minoru Ozeki, Masayuki Yamashita
  • Journal Title: Tetrahedron Lett. Volume: 52 Pages: 7046-7048
  • DOI: 10.1016/j.tetlet.2011.10.018
  • Peer Reviewed
• [Journal Article] The First total syntheses of (+)-hostmanin A and (+)-methyllinderatin (2011)
  • Author(s): Junko Kitao, Naoko Kitamura, Nozomi Kumo, Kenji Arimitsu, Hiroki Iwasaki, Minoru Ozeki, Ai Kurume, Masayuki Yamashita
  • Journal Title: Heterocycles Volume: 83 Pages: 143-151
  • DOI: 10.3987/COM-10-12084
  • Peer Reviewed
• [Presentation] 非対称ベンジルケトン体から5-アリール-α-ピロン体の改良合成法 (2014)
  • Author(s): 三浦拓也,藤岡咲,竹村直人,小島直人,岩崎宏樹,小関稔,山下正行
  • Organizer: 日本薬学会第134年会
  • Place of Presentation: 熊本
  • Year and Date: 20140300
• [Presentation] Cyclopenta[b]benzofuran-3-one体のtetrahydrodibenzofuran体への環拡大反応 (2014)
  • Author(s): 山本卓,伊藤健史,原川牧子,宮上康徳,齋藤興輝,松井優子,有光健治,小島直人,岩崎宏樹,小関稔,山下正行
  • Organizer: 日本薬学会第134年会
  • Place of Presentation: 熊本
  • Year and Date: 20140300
• [Presentation] 5位アリール基により誘起されるα-ピロン体から縮環型ジヒドロピラン体への骨格変換反応 (2014)
  • Author(s): 山下正行,三浦拓也,藤岡咲,竹村直人,小島直人,岩崎宏樹,小関稔
  • Organizer: 日本薬学会第134年会
  • Place of Presentation: 熊本
  • Year and Date: 20140300
• [Presentation] α-ピロンと硫黄イリドから生成するシクロプロパン中間体の開環を伴う骨格変換反応 (2013)
  • Author(s): 三浦拓也,藤岡咲,Navnath Dnyanoba Yadav,岩崎宏樹,小関稔,小島直人,山下正行
  • Organizer: 第43回複素環化学討論会講演
  • Place of Presentation: 岐阜
  • Year and Date: 20131000
• [Presentation] 5-アリール-3-アルコキシカルボニル-α-ピロン誘導体の改良合成法の開発 (2013)
  • Author(s): 藤岡咲,三浦拓也,竹村直人,岩崎宏樹,小関稔,小島直人,山下正行
  • Organizer: 第63回日本薬学会近畿支部総会・大会
  • Place of Presentation: 京田辺
  • Year and Date: 20131000
• [Presentation] 5位アリール基の置換基効果により縮環型ジヒドロフランを構築する骨格変換反応の開発 (2013)
  • Author(s): 三浦拓也,藤岡咲,竹村直人,岩崎宏樹,小関稔,小島直人,山下正行
  • Organizer: 第63回日本薬学会近畿支部総会・大会
  • Place of Presentation: 京田辺
  • Year and Date: 20131000
• [Presentation] 連続的炭素-炭素結合形成・切断によりビシクロ[3.1.0]ヘキサンを構築する新規骨格変換反応の開発 (2013)
  • Author(s): 三浦拓也,藤岡咲,Navnath Dnyanoba Yadav,岩崎宏樹,小関稔,小島直人,山下正行
  • Organizer: 日本薬学会第133年会
  • Place of Presentation: 横浜
  • Year and Date: 20130300
• [Presentation] 縮還型α-ピロンからスピロビシクロ[3.1.0]ヘキサン誘導体へのタンデム骨格変換反応の開発研究 (2012)
  • Author(s): 三浦拓也,Navnath Dnyanoba Yadav,藤岡咲,岩崎宏樹,小関稔,小島直人,山下正行
  • Organizer: 第38回反応と合成の進歩シンポジウム-ライフサイエンスを志向した理論、反応および合成-
  • Place of Presentation: 東京
  • Year and Date: 20121100
• [Presentation] 骨格変換反応によるスピロビシクロ[3.1.0]ヘキサン誘導体の新規合成法の開発 (2012)
  • Author(s): 三浦拓也,Navnath Dnyanoba Yadav,藤岡咲,岩崎宏樹,小関稔,小島直人,山下正行
  • Organizer: 第62回日本薬学会近畿支部総会・大会
  • Place of Presentation: 西宮
  • Year and Date: 20121000
• [Presentation] Adunctin Bの全合成 (2011)
  • Author(s): 有光健治、野村沙代、小菅裕也、乾尚之、坂田裕介、藤田由季恵、伊藤健史、原川牧子、岩崎宏樹、小関稔、山下正行
  • Organizer: 第37回反応と合成の進歩シンポジウム-ライフサイエンスを志向した理論、反応および合成-
  • Place of Presentation: 徳島
  • Year and Date: 20111100
• [Presentation] (±)-Adunctin Bの全合成 (2011)
  • Author(s): 乾尚之、有光健治、野村沙代、小菅裕也、坂田裕介、藤田由季恵、伊藤健史、原川牧子、岩崎宏樹、小関稔、山下正行
  • Organizer: 第61回日本薬学会近畿支部総会・大会
  • Place of Presentation: 兵庫
  • Year and Date: 20111000
• [Presentation] Adunctin Bの全合成 (2011)
  • Author(s): 有光健治、野村沙代、小菅裕也、乾尚之、坂田裕介、藤田由季恵、伊藤健史、原川牧子、岩崎宏樹、小関稔、細井信造、山下正行
  • Organizer: 日本薬学会第131年会
  • Place of Presentation: 静岡
  • Year and Date: 20110300
• [Presentation] Adunctin Bの合成研究 (2010)
  • Author(s): 有光健治、野村沙代、小菅裕也、乾尚之、坂田裕介、藤田由季恵、岩崎宏樹、小関稔、細井信造、山下正行
  • Organizer: 第60回日本薬学会近畿支部総会・大会
  • Place of Presentation: 大阪
  • Year and Date: 20101000