Asymmetric hydroxylation based on the Lewis acid-induced weak interaction and its application to the synthesis of natural products

• Project/Area Number: 18550031
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Organic chemistry
• Research Institution: Shizuoka University
• Principal Investigator: YODA Hidemi Shizuoka University, 工学部, 教授 (20201072)
• Project Period (FY): 2006 – 2008
• Project Status: Completed (Fiscal Year 2008)
• Budget Amount: ¥4,270,000 (Direct Cost: ¥3,700,000、Indirect Cost: ¥570,000); Fiscal Year 2008: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000); Fiscal Year 2007: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000); Fiscal Year 2006: ¥1,800,000 (Direct Cost: ¥1,800,000)
• Keywords: ラクタム / イオウ置換基 / 脱硫反応 / ルイス酸触媒 / ヒドロキシル化

Research Abstract

芳香族あるいは脂肪族を問わず、γ-位にイオウ置換基を持つラクタムがLewis酸性の低い金属塩のみが存在する水溶液中において、これまでにまったく未知な脱硫-ヒドロキシル化反応を行い、開環反応を伴わずに4級炭素を含むヒドロキシラクタム類を与えることを見い出した。そこでこれらの反応性を詳細に検討し、水溶液中での弱い配位環境に基づく不斉脱硫-ヒドロキシル化反応の発現に成功した。ついでこの反応を利用して、チリ産の植物ヘビノボラスより単離され、強い健胃作用を有するlennoxamineを中心とした生理活性天然物の全合成に成功した。

Research Products

• [Journal Article] Stereodivergent Synthesis of New Amino Sugars, Furanodictine A and B, Starting from D-glucuronolactone (2008)
  • Author(s): Daisuke Matsuura, Takeshi Mitsui, Tetsuya Sengoku, Masaki Takahashi and Hidemi Yoda
  • Journal Title: Tetrahedron 64 Pages: 11686-11696
• [Journal Article] First Asymmetric Synthesis of Pyrrolizidine Alkaloids, (+)-Hyacinthacine B1 and(+)-B2 (2008)
  • Author(s): Tetsuya Sengoku, Yasutaka Satoh, Manami Oshima, Masaki Takahashi, Hidemi Yoda
  • Journal Title: Tetrahedron 64 Pages: 8052-8058
• [Journal Article] Catalytic Enantioselective Allylation of Aldehydes Using β-Amido Functionalized Allylstannanes with Chiral In(Otf)_3/i-Pr-pybox Complexes (2008)
  • Author(s): Takamasa Suzuki, Tetsuya Sengoku, Masaki Takahashi and Hidemi Yoda
  • Journal Title: Tetrahedron Letters 49 Pages: 4701-4703
  • URL: http://hdl.handle.net/10297/2602
• [Journal Article] New Asymmetric Strategy for the Total Synthesis of Naturally Occurring(+)-Alexine and(-)-7-Epi-alexine (2008)
  • Author(s): Nasaki Takahashi, Tetsuya Maenara, Tetsuya Dengoku, Norifumi Fujita, Kunihiko Takabe and Hidemi Yoda
  • Journal Title: Tetrahedron 64 Pages: 5254-5261
  • NAID: 120000796413
  • URL: http://hdl.handle.net/10297/2466
• [Journal Article] Mechanistic Investigation of Energy Transfer in Perylene-cored Anthracene Dendrimers (2008)
  • Author(s): Masaki Takahashi, Hironao Morimoto, Kentaro Miyake, Hideki Kawai, Yoshihisa Sei, Kentaro Yamaguchi, Mitsuji Yamashita, Tetsuya Sengokua and Hidemi Yoda
  • Journal Title: New Journal Chemistry 32 Pages: 547-553
• [Journal Article] A Practical Synthesis of(E)-2-Cyclopentadecen-1-one : An Important Precursor of Macrocyclic Muscone (2008)
  • Author(s): Yusuke Hisanaga, Yuya Asumi, Masaki Takahashi, Yasuhiro Shimizu, Nobuyuki Mase, Hidemi Yoda and Kunihiko Takabe
  • Journal Title: Tetrahedron Letters 49 Pages: 548-551
• [Journal Article] Mechanistic Investigation of Energy Transfer in Perylene-cored Anthracene Dendrimers (2008)
  • Author(s): Masaki Takahashi
  • Journal Title: New Journal of Chemistry 32 Pages: 547-553
  • Peer Reviewed
• [Journal Article] New Asymmetric Strategy for the Total Synthesis of Naturally Occurring (+)-Alexine and (-)-7-Epi-alexine (2008)
  • Author(s): Masaki Takahashi
  • Journal Title: Tetrahedron 64 Pages: 5254-5261
  • Peer Reviewed
• [Journal Article] Catalytic Enantioselective Allylation of Aldehydes Using β-Amido Functionalized Allylstannanes with Chiral In(OTf)_3/i-Pr-pybox Complexes (2008)
  • Author(s): Takamasa Suzuki
  • Journal Title: Tetrahedron Letters 49 Pages: 4701-4703
  • Peer Reviewed
• [Journal Article] First Asymmetric Synthesis of Pyrrolizidine Alkaloids, (+)-Hyacinthacine B_1 and (+)-B_2 (2008)
  • Author(s): Tetsuya Sengoku
  • Journal Title: Tetrahedron 64 Pages: 8052-8058
  • Peer Reviewed
• [Journal Article] Stereodivergent Synthesis of New Amino Sugars, Furanodictine A and B, Starting from D-glucuronolactone (2008)
  • Author(s): Daisuke Matsuura
  • Journal Title: Tetrahedron 64 Pages: 11686-11696
  • Peer Reviewed
• [Journal Article] A Practical synthesis of (E)-2-Cyclopentadecen-1-one:An Important Precursor of Macrocyclic Muscone (2008)
  • Author(s): Yusuke Hisanaga
  • Journal Title: Tetrahedron Letters 49 Pages: 548-551
  • Peer Reviewed
• [Journal Article] Total Synthesis of (-)-2-epi-Lentiginosine by use of Chiral 5-Hydroxy-1,5- dihydropyrrol-2-one as a Building Block (2007)
  • Author(s): Takayuki Muramatsu, Sho Yamashita, Yumiko Nakamura, Masahisa Suzuki, Nobuyuki Mase, Hidemi Yoda and Kunihiko Takabe
  • Journal Title: Tetrahedron Letters 48 Pages: 8956-8959
• [Journal Article] First Total Syntheses of New Phenylpropanoid Lignans, (±)-Aglacin K Stereoisomer and(±)-Arborone (2007)
  • Author(s): Masaki Takahashi, Koji Takada, Daisuke Matsuura, Kunihiko Takabe, and Hidemi Yoda
  • Journal Title: Heterocycles 71 Pages: 2113-2118
• [Journal Article] Total Synthesis of(-)-2-epi-Lentiginosine by use of Chiral5-Hydroxy-1,5-dihydropyrrol-2-one as a Building Block (2007)
  • Author(s): Takayuki Muramatsu
  • Journal Title: Tetrahedron Letters 48 Pages: 8956-8959
  • Peer Reviewed
• [Journal Article] First Total Syntheses of New Phenylpropanoid Lignans,(±)-Aglacin K S tereoisomer and (±)-Arborone (2007)
  • Author(s): Masaki Takahashi
  • Journal Title: Heterocycles 71 Pages: 2113-2118
  • Peer Reviewed
• [Journal Article] Novel Chemoselective Desulfurization of γ-Phenylthio-substituted Aromatic Lactams: Application to the Synthesis of Isoindolobenzazepine Alkaloid (2006)
  • Author(s): Lennoxamine Takamasa Suzuki, Kunihiko Takabe, Hidemi Yoda
  • Journal Title: Synlett Pages: 3407-3410
• [Journal Article] Lipase-catalyzed Kinetic Resolution of Tetronic Acid Derivatives Bearing a Chiral Quaternary Carbon : Total Synthesis of(S)-(-)-Vertinolide (2006)
  • Author(s): Tetsuo Tauchi, Hiroki Sakuma, Takahiro Ohno, Nobuyuki Mase, Hidemi Yoda and Kunihiko Takabe
  • Journal Title: Tetrahedron Asymmetry 17 Pages: 2195-2198
• [Journal Article] Lipase-catalyzed Kinetic Resolution of Thiotetronic Acid Derivatives Bearing a Chiral Quaternary Carbon : Total Synthesis of R-Thiolactomycin and Its O-analogue (2006)
  • Author(s): Ken-ichi Toyama, Tetsuo Tauchi, Nobuyuki Mase, Hidemi Yoda and Kunihiko Takabe
  • Journal Title: Tetrahedron Letters 47 Pages: 7163-7166
• [Journal Article] First Asymmetric Synthesis of New Diarylheptanoids, Renealtin A and B, with a Tetrahydrofuran Ring (2006)
  • Author(s): Tomoki Katoh, Daisuke Matsuura, Nobuyuki Mase, Kunihiko Takabe, and Hidemi Yoda
  • Journal Title: Synlett Pages: 2031-2034
• [Journal Article] Organocatalytic Direct Michael Reaction of Ketones and Aldehydes with β-nitrostyrene in brine (2006)
  • Author(s): Nobuyuki Mase, Kaori Watanabe, Hidemi Yoda, Kunihiko Takabe, Fujie Tanaka, and Carlos F
  • Journal Title: Barbas III, J. Am. Chem .Soc 128 Pages: 4966-4967
• [Journal Article] Novel and Stereocontrolled Asymmetric Synthesis of a New Naturally Occurring Styryllactone, (+)-Cardiobutanolide (2006)
  • Author(s): Daisuke Matsuura, Kunihiko Takabe and Hidemi Yoda
  • Journal Title: Tetrahedron Letters 47 Pages: 1371-1374
• [Journal Article] SmI_2-promoted Novel Tandem Elimination and Coupling Reactions of Aliphatic Imides with Carbonyl Compounds; Application to the Synthesis of dl-Isoretronecanol (2006)
  • Author(s): Masayuki Kabata, Takamasa Suzuki, Kunihiko Takabe and Hidemi Yoda
  • Journal Title: Tetrahedron Letters 47 Pages: 1607-1611
• [Journal Article] Organocatalytic Direct Asymmetric Aldol Reactions in Water (2006)
  • Author(s): Nobuyuki. Mase, Yusuke. Nakai, Naoko. Ohara, Hidemi. Yoda, Kunihiko. Takabe, Fujie Tanaka, and Carlos F. Barbas III
  • Journal Title: J. Am. Chem .Soc 128 Pages: 734-735
• [Journal Article] Novel Chemoselective Desulfurization of γ-Phenylthio-substituted Aromatic Lactams : Application to the Synthesis of Isoindolobenzazepine Alkaloid, Lennoxamine (2006)
  • Author(s): Takamasa Suzuki
  • Journal Title: Synlett (20) Pages: 3407-3410
• [Journal Article] Lipase-catalyzed Kinetic Resolution of Tetronic Acid Derivatives Bearing a Chiral Quaternary Carbon : Total Synthesis of (S)-(- )- Vertinolide (2006)
  • Author(s): Tetsuo Tauchi
  • Journal Title: Tetrahedron : Asymmetry 17 Pages: 2195-2198
• [Journal Article] SmI_2-promoted novel tandem elimination and coupling reactions of aliphatic imides with carbonyl compounds; application to the synthesis of dl-isoretronecanol (2006)
  • Author(s): Masayuki Kabata
  • Journal Title: Tetrahedron Letters 47 Pages: 1607-1611
• [Journal Article] Organocatalytic Direct Michael Reaction of Ketones and Aldehydes with β-nitrostyrene in brine (2006)
  • Author(s): Nobuyuki Mase
  • Journal Title: J. Am. Chem. Soc. 128 Pages: 4966-4967
• [Journal Article] Novel and stereocontrolled asymmetric synthesis of a new naturally occurring styryllactone, (+)-cardiobutanolide (2006)
  • Author(s): Daisuke Matsuura
  • Journal Title: Tetrahedron Letters 47 Pages: 1371-1374
• [Journal Article] Organocatalytic Direct Asymmetric Aldol Reactions in Water (2006)
  • Author(s): Nobuyuki Mase
  • Journal Title: J. Am. Chem. Soc. 128 Pages: 734-735
• [Presentation] 色素逆ミセル空間を利用した金ナノ粒子の自発的形成 (2009)
  • Author(s): 高橋雅樹, 大野修平, 仙石哲也, 依田秀実
  • Organizer: 日本化学会第89春季年会
  • Place of Presentation: 日本大学
  • Year and Date: 2009-03-29
• [Presentation] 色素逆ミセル空間を利用した金ナノ粒子の自発的形成 (2009)
  • Author(s): 高橋雅樹
  • Organizer: 日本化学会第89春季年会
  • Place of Presentation: 日本大学船橋キャンパス
  • Year and Date: 2009-03-29
• [Presentation] ルイス酸による位置選択的ジアステレオ選択的反応を用いたmacronecineの合成研究 (2008)
  • Author(s): 仙石哲也, 柿本達郎, 鈴木崇将, 高橋雅樹, 依田秀実
  • Organizer: 第38回複素環化学討論会
  • Place of Presentation: 福山
  • Year and Date: 2008-11-23
• [Presentation] ルイス酸による位置選択的、ジアステレオ選択的反応を用いたmacronecineの合成研究 (2008)
  • Author(s): 仙石哲也
  • Organizer: 第38回複素環化学討論会
  • Place of Presentation: 福山市
  • Year and Date: 2008-11-23
• [Presentation] 海綿由来の新規アルカロイドbatzellasideBの合成研究 (2008)
  • Author(s): 大嶋麻奈未, 仙石哲也, 高橋雅樹, 依田秀実
  • Organizer: 第39回中部化学関係学協会支部連合秋季大会
  • Place of Presentation: 名古屋
  • Year and Date: 2008-11-09
• [Presentation] 海綿由来の新規アルカロイドbatzellaside Bの合成研究 (2008)
  • Author(s): 大嶋麻奈未
  • Organizer: 第39回中部化学関係学協会支部連合秋季大会
  • Place of Presentation: 名古屋大学
  • Year and Date: 2008-11-09
• [Presentation] ローダミン色素を担持した光捕集デンドリマーの開発 (2008)
  • Author(s): 高橋雅樹, 川井秀記, 仙石哲也, 依田秀実
  • Organizer: 第57回高分子討論会
  • Place of Presentation: 大阪市立大学
  • Year and Date: 2008-09-25
• [Presentation] 金ナノ粒子を内包した色素逆ミセル集合体のコロイド合成 (2008)
  • Author(s): 高橋雅樹
  • Organizer: 第57回高分子討論会
  • Place of Presentation: 大阪市立大学
  • Year and Date: 2008-09-24
• [Presentation] 中心にアミノ基を有する色素分子の四塩化金酸添加による逆ミセル形成と金ナノ粒子合成 (2008)
  • Author(s): 高橋雅樹
  • Organizer: 光化学討論会
  • Place of Presentation: 大阪府立大学
  • Year and Date: 2008-09-17
• [Presentation] Takamasa Suzuki, Tetsuya Sengoku, Masaki Takahashi and Hidemi Yoda (2008)
  • Author(s): Enantioselective Allylation of Aldehydes Employing β-Amido Allylstannanes Catalyzed by Chiral In(Otf)3/i-Pr-pybox Complexes
  • Organizer: 9th Tetrahedron
  • Place of Presentation: Symposium, Berkeley, CA, USA
  • Year and Date: 2008-07-01
• [Presentation] 新規なピロリジジンアルカロイドHyacinthacineC2, C3の不斉合成研究 (2008)
  • Author(s): 佐藤康任
  • Organizer: 日本化学会第89春季年会
  • Place of Presentation: 日本大学船橋キャンパス
  • Year and Date: 2008-03-29
• [Presentation] Novel Synthetic Studies of a New Polyketide Natural Product, Cryptomoscatone D_2 (2007)
  • Author(s): Daisuke Matsuura
  • Organizer: The 2007 21st International Congress of Heterocyclic Chemistry
  • Place of Presentation: Sydney(Australia)
  • Year and Date: 2007-07-16
• [Remarks]
  • URL: http://www.ipc.shizuoka.ac.jp/~tchyoda/index.html