Development of organocatalysis aiming for the preparation of important synthetic intermediates

• Project/Area Number: 21550106
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Synthetic chemistry
• Research Institution: University of Shizuoka
• Principal Investigator: SUZUKI Yumiko 静岡県立大学, 薬学部, 講師 (20295546)
• Project Period (FY): 2009 – 2011
• Project Status: Completed (Fiscal Year 2011)
• Budget Amount: ¥4,810,000 (Direct Cost: ¥3,700,000、Indirect Cost: ¥1,110,000); Fiscal Year 2011: ¥910,000 (Direct Cost: ¥700,000、Indirect Cost: ¥210,000); Fiscal Year 2010: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000); Fiscal Year 2009: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
• Keywords: 不斉合成・反応 / 触媒設計・反応 / 環境調和型反応 / 選択的合成・反応 / 有機触媒反応

Research Abstract

An efficient one-pot synthesis of various unsymmetrical benzils and heterocycles has been developed. NHC-catalyzed aroylation of N-phenylimidoyl chlorides with aromatic aldehydes followed by acidic hydrolysis gives benzils. A one-pot synthesis of quinoxalines and pyrazines by condensation/cyclization reaction of unsymmetrical benzils generated in situ with diamines was also achieved.
Novel C_2-symmetrical imidazolium salts were synthesized and used in kinetic resolution of secondary alcohols and in asymmetric cyanosilylation as a catalyst precursor. It was found out that substituents at 4-and 5-position of imidazole increase the reaction rates.

Research Products

• [Journal Article] Synthesis of unsymmetrical benzils using N-heterocyclic carbine catalysis (2011)
  • Author(s): Yumiko Suzuki, Abu Bakar Md., Takashi Tanoi, Naoko Nomura, and Masayuki Sato
  • Journal Title: Tetrahedron Volume: 67 Issue: 25 Pages: 4710-4715
  • DOI: 10.1016/j.tet.2011.04.020
• [Journal Article] Xanthone natural products via N-heterocyclic carbene catalysis : Total synthesis of atroviridin (2011)
  • Author(s): Yumiko Suzuki, Yoshinori Fukuta, Shinya Ota, Masayo Kamiya, and Masayuki Sato
  • Journal Title: J. Org. Chem Volume: 76 Pages: 3960-3967
  • URL: http://pubs.acs.org/doi/pdf/10.1021/jo200303c
• [Journal Article] Xanthone Natural Products via N-Heterocyclic Carbene Catalysis : Total Synthesis of Atroviridin (2011)
  • Author(s): Yumiko Suzuki
  • Journal Title: The Journal of Organic Chemistry Volume: 76(未定)
  • Peer Reviewed
• [Journal Article] Synthesis of unsymmetrical benzils using N-heterocyclic carbene catalysis (2011)
  • Author(s): Yumiko Suzuki
  • Journal Title: Tetrahedron Volume: 67(未定)
  • Peer Reviewed
• [Journal Article] A one-pot synthesis of 3-arylglutaric anhydrides by reaction of ketene with aromatic aldehydes and ketones (2009)
  • Author(s): Hirokazu Matsunaga, Kiyoshi Ikeda, Ken-ichi Iwamoto, Yumiko Suzuki, Masayuki Sato
  • Journal Title: Tetrahedron Lett Volume: 50 Issue: 20 Pages: 2334-2336
  • DOI: 10.1016/j.tetlet.2009.02.193
  • Peer Reviewed
• [Journal Article] A one-pot synthesis of 3-arylglutaric anhydrides by reaction of ketene with aromatic aldehdes and ketones (2009)
  • Author(s): Hirokazu Matsunaga
  • Journal Title: Tetrahedron Letters Vol.50 Pages: 2334-2336
  • Peer Reviewed
• [Presentation] 非対称ベンジルおよび含窒素複素環式化合物のone-pot合成 (2012)
  • Author(s): 室伏舞、眞鍋敬、鈴木由美子
  • Organizer: 日本薬学会第132回年会
  • Place of Presentation: 札幌
  • Year and Date: 2012-03-31
• [Presentation] 位置選択的Claisen転位反応およびNHC触媒反応を利用したtermicalcicolanone Aの合成研究 (2011)
  • Author(s): 鈴木由美子、北村太樹、眞鍋敬
  • Organizer: 第42回中部化学関係学協会支部連合秋季大会
  • Place of Presentation: 長野
  • Year and Date: 2011-11-05
• [Presentation] 位置選択的Claisen転位反応およびNHC触媒反応を利用したtermicalcicolan one Aの合成研究 (2011)
  • Author(s): 北村太樹
  • Organizer: 第42回中部化学関係学協会支部連合秋季大会
  • Place of Presentation: 長野
  • Year and Date: 2011-11-05
• [Presentation] 含窒素複素環式カルベンの触媒反応を利用した非対称ベンジルのone-pot合成 (2011)
  • Author(s): 室伏舞、眞鍋敬、鈴木由美子
  • Organizer: 第57回日本薬学会東海支部大会
  • Place of Presentation: 名古屋
  • Year and Date: 2011-07-09
• [Presentation] がん細胞増殖阻害活性を示すキナゾリン誘導体の合成研究 (2011)
  • Author(s): 大竹亜耶奈、鈴木由美子、石井浩介、松野研司、浅井章良、眞鍋敬
  • Organizer: 日本薬学会第131年会
  • Place of Presentation: 静岡
  • Year and Date: 2011-03-31
• [Presentation] 位置選択的Claisen転位反応を用いるtermicalcicolanone Aの合成研究 (2011)
  • Author(s): 北村太樹、鈴木由美子、眞鍋敬
  • Organizer: 日本薬学会第131年会
  • Place of Presentation: 静岡
  • Year and Date: 2011-03-29
• [Presentation] 位置選択的Claisen転位を用いるtermicalcicolanone Aの合成研究 (2011)
  • Author(s): 鈴木由美子
  • Organizer: 日本薬学会第131年会
  • Place of Presentation: 静岡
  • Year and Date: 2011-03-29
• [Presentation] Termicalcicolanone Aの合成研究 (2010)
  • Author(s): 鈴木由美子、北村太樹、眞鍋敬
  • Organizer: 平成22年度日本薬学会東海支部例会
  • Place of Presentation: 静岡
  • Year and Date: 2010-11-28
• [Presentation] 複素環式カルベンの触媒反応を用いた天然キサントン化合物の合成研究 (2010)
  • Author(s): 鈴木由美子、宇都宮崇広、北村大樹、福田吉則、太田慎也、神谷昌代、佐藤雅之、眞鍋敬
  • Organizer: 第36回反応と合成の進歩シンポジウム
  • Place of Presentation: 名古屋
  • Year and Date: 2010-11-01
• [Presentation] 有機触媒反応を利用したキサントン天然物の合成研究 (2010)
  • Author(s): 宇都宮崇広、福田吉則、太田慎也、佐藤雅之、眞鍋敬、鈴木由美子
  • Organizer: 第52回天然有機化合物討論会
  • Place of Presentation: 静岡
  • Year and Date: 2010-09-29
• [Presentation] Termicalcicolanone の全合成研究 (2010)
  • Author(s): 宇都宮崇広
  • Organizer: 日本薬学会第130年会
  • Place of Presentation: 岡山
  • Year and Date: 2010-03-28
• [Presentation] Termicalcicolanone Bの合成研究 (2010)
  • Author(s): 宇都宮崇弘、眞鍋敬、鈴木由美子
  • Organizer: 日本薬学会第130年会
  • Year and Date: 2010-03-26
• [Presentation] Termicalcicolanone A, Bの合成研究 (2010)
  • Author(s): 宇都宮崇広、北村太樹、眞鍋敬、鈴木由美子
  • Organizer: 第40回複素環化学討論会
  • Place of Presentation: 仙台
• [Presentation] 含窒素複素環式カルベン触媒によるジアリルケトンの合成とその天然物合成への利用 (2009)
  • Author(s): 鈴木由美子、福田吉則、太田慎也、上田雄貴、佐藤雅之
  • Organizer: 第35回反応と合成の進歩シンポジウム
  • Place of Presentation: 金沢
  • Year and Date: 2009-11-16
• [Presentation] 含窒素複素環式カルベンの触媒反応を利用した非対称1, 2-ジケトンの合成 (2009)
  • Author(s): 鈴木由美子、野村奈生子、Md. Abu Bakar、田野井隆、佐藤雅之
  • Organizer: 第2回有機触媒シンポジウム
  • Place of Presentation: 京都
  • Year and Date: 2009-09-28
• [Presentation] 含窒素複素環式カルベンの触媒反応を利用した非対称1,2-ジケトンの合成 (2009)
  • Author(s): 鈴木由美子
  • Organizer: 第2回有機触媒シンポジウム
  • Place of Presentation: 京都
  • Year and Date: 2009-09-28
• [Presentation] 含窒素複素環式カルベンの触媒反応を利用したatroviridinの全合成 (2009)
  • Author(s): 鈴木由美子、福田吉則、太田慎也、佐藤雅之
  • Organizer: 第26回有機合成化学セミナー
  • Place of Presentation: 前橋
  • Year and Date: 2009-09-16
• [Presentation] 含窒素複素環式カルベンの触媒反応を利用した atroviridin の全合成 (2009)
  • Author(s): 鈴木由美子
  • Organizer: 第26回有機合成化学セミナー
  • Place of Presentation: 前橋
  • Year and Date: 2009-09-16
• [Presentation] 有機触媒としての含窒素複素環式カルベン―反応開発と合成への利用― (2009)
  • Author(s): 鈴木由美子
  • Organizer: 平成21年度有機合成協会東海支部 有機合成セミナー
  • Place of Presentation: 静岡
  • Year and Date: 2009-09-12
• [Presentation] Total Synthesis of Atroviridin using Nucleophilic Acylation Catalyzed by N-Heterocyclic Carbene (2009)
  • Author(s): Yumiko Suzuki, Yoshinori Fukuta, Shinya Ota, Masayuki Sato
  • Organizer: The 5th Japan-Korea Young Scientists Meeting on Bioorganic and Natural Products Chemistry
  • Place of Presentation: Yugawara
  • Year and Date: 2009-08-28
• [Presentation] Total synthesis of atroviridin using nucleophilic acylation catalyzed by N-heterocyclic carbene (2009)
  • Author(s): 鈴木由美子
  • Organizer: The 5th Japan-Korea Young Scientists Meeting on Bio-organic and Natural Products Chemistry
  • Place of Presentation: Yugawara
  • Year and Date: 2009-08-28
• [Presentation] New synthetic approach to xanthone natural products using N-heterocyclic carbene catalysis (2009)
  • Author(s): Yumiko Suzuki, Yoshinori Fukuta, Shinya Ota, Yuki Ueda, Masayuki Sato
  • Organizer: 22nd International Congress on Heterocyclic Chemistry
  • Place of Presentation: Canada
  • Year and Date: 2009-08-06
• [Presentation] New synthetic approach to xanthone natural products using N-heterocyclic carbene catalysis (2009)
  • Author(s): 鈴木由美子
  • Organizer: 22nd International Congress on Heterocyclic Chemistry
  • Place of Presentation: St.John's, Canada
  • Year and Date: 2009-08-06
• [Presentation] Atroviridinの全合成 (2009)
  • Author(s): 鈴木由美子
  • Organizer: 2008 USフォーラム
  • Place of Presentation: 静岡
  • Year and Date: 2009-08-05
• [Presentation] Highly efficient synthesis of 2, 5-or 2, 6-bridged pyridine : intramolecular[4+2] cycloaddition of bis(acylketene) followed by ring transformation (2009)
  • Author(s): Masayuki Sato, Kie Suwa, Katsuya Fusazaki, Yasuko Morie, Kiyoshi Ikeda, Yumiko Suzuki, Ken-ichi Iwamoto
  • Organizer: 22nd International Congress on Heterocyclic Chemistry
  • Place of Presentation: Canada
  • Year and Date: 2009-08-04
• [Presentation] Highly efficient synthesis of 2, 5-or 2, 6-bridged pyridine : intramolecular[4+2]cycloaddition of bis(acylketene) followed by ring transformation (2009)
  • Author(s): Masayuki Sato
  • Organizer: 22nd International Congress on Heterocyclic Chemistry
  • Place of Presentation: St.John's, Canada
  • Year and Date: 2009-08-04
• [Remarks]
• [Remarks]
  • URL: http://www.u-shizuoka-ken.ac.jp/
• [Patent(Industrial Property Rights)] キナゾリン化合物を有効成分とする医薬組成物 (2010)
  • Inventor(s): 浅井章良,澤田潤一,松野研司,鈴木由美子
  • Industrial Property Rights Holder: 浅井章良,澤田潤一,松野研司,鈴木由美子
  • Industrial Property Number: 2010-046911
  • Filing Date: 2010-03-05