Site-Selevctive Molecular Transformation based on Activation of Catalytic Intermediate via Counterion Exchange

• Project/Area Number: 15K18827
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Multi-year Fund
• Research Field: Chemical pharmacy
• Research Institution: Kyoto University
• Principal Investigator: Ueda Yoshihiro 京都大学, 化学研究所, 助教 (90751959)
• Project Period (FY): 2015-04-01 – 2017-03-31
• Project Status: Completed (Fiscal Year 2016)
• Budget Amount: ¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000); Fiscal Year 2016: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000); Fiscal Year 2015: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
• Keywords: 求核触媒 / カウンターアニオン / 位置選択性 / 有機化学 / 有機分子触媒 / アシル化 / 不斉非対称化 / 合成化学 / 糖 / ポリアミン

Outline of Final Research Achievements

We have proposed a new catalytic cycle for catalytic site-selective acylation of a carbohydrate based on quantitative analysis of reactivity of the catalytic intermediate. Catalyst loading was successfully decreased from 10 mol% to less than 0.1 mol%. Introduction of various substituted benzoyl groups were achieved site-selectively, which indicate that the reaction is applicable for efficient total synthesis of natural glycosides.

Research Products

• [Journal Article] Organocatalytic Chemoselective Monoacylation of 1,n-Linear Disulfonamides (2017)
  • Author(s): Keisuke Yoshida, Atsushi Hirata, Hisashi Hashimoto, Ayumi Imayoshi, Yoshihiro Ueda, Takumi Furuta, Takeo Kawabata
  • Journal Title: Tetrahedron Letters Volume: 58 Issue: 11 Pages: 1030-1033
  • DOI: 10.1016/j.tetlet.2017.01.039
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Total Synthesis of Ellagitannins <i>via</i> Sequential Site-Selective Functionalization of Unprotected D-Glucose (2017)
  • Author(s): Hironori Takeuchi, Yoshihiro Ueda, Takumi Furuta, Takeo Kawabata
  • Journal Title: Chemical and Pharmaceutical Bulletin Volume: 65 Issue: 1 Pages: 25-32
  • DOI: 10.1248/cpb.c16-00436
  • NAID: 130005187627
  • ISSN: 0009-2363, 1347-5223
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Final-stage Site-selective Acylation for the Total Synthesis of Natural Glycosides (2016)
  • Author(s): Yoshihiro Ueda
  • Journal Title: YAKUGAKU ZASSHI Volume: 136 Issue: 12 Pages: 1631-1639
  • DOI: 10.1248/yakushi.16-00186
  • NAID: 130005170248
  • ISSN: 0031-6903, 1347-5231
  • Year and Date: 2016-12-01
  • Peer Reviewed
• [Journal Article] Organocatalytic Site-Selective Acylation of Avermectin B_2a, a Unique Endectocidal Drug (2016)
  • Author(s): Takeshi Yamada, Koh Suzuki, Tomoyasu Hirose, Takumi Furuta, Yoshihiro Ueda, Takeo Kawabata, Satoshi Omura and Toshiaki Sunazuka
  • Journal Title: Chemical and Pharmaceutical Bulletin Volume: 64 Issue: 7 Pages: 856-864
  • DOI: 10.1248/cpb.c16-00205
  • NAID: 130005160046
  • ISSN: 0009-2363, 1347-5223
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Organocatalytic Site-Selective Acylation of 10-Deacetylbaccatin III (2016)
  • Author(s): Yanagi Masanori, Ryo Ninomiya, Yoshihiro Ueda, Takumi Furuta, Takeshi Yamada, Toshiaki Sunazuka, Takeo Kawabata
  • Journal Title: Chemical and Pharmaceutical Bulletin Volume: 64 Issue: 7 Pages: 907-912
  • DOI: 10.1248/cpb.c16-00037
  • NAID: 130005160042
  • ISSN: 0009-2363, 1347-5223
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Catalyst-controlled regiodivergent vinylogous aza-Morita-Baylis-Hillman reactions (2016)
  • Author(s): Hyakutake, R.; Gondo, N.; Ueda, Y.; Yoshimura, T.; Furuta, T.; Kawabata, T.
  • Journal Title: Tetrahedron Lett. Volume: 57 Issue: 12 Pages: 1321-1324
  • DOI: 10.1016/j.tetlet.2016.02.029
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Insights into the Molecular Recognition Process in Organocatalytic Chemoselective Monoacylation of 1,5-Pentanediol (2016)
  • Author(s): Ayumi Imayoshi, Masahiro Yamanaka, Makoto Sato, Keisuke Yoshida, Takumi Furuta, Yoshihiro Ueda and Takeo Kawabata
  • Journal Title: Advanced Synthesis and Catalysis Volume: - Issue: 8 Pages: 1337-1344
  • DOI: 10.1002/adsc.201600010
  • Peer Reviewed
• [Journal Article] Organocatalytic Site-Selective Acylation of Carbohydrates and Polyol Compounds (2016)
  • Author(s): Yoshihiro Ueda, Takeo Kawabata
  • Journal Title: Topics in Current Chemistry Volume: 372 Pages: 203-231
  • DOI: 10.1007/128_2015_662
  • ISBN: 9783319263311, 9783319263335
  • Peer Reviewed
• [Journal Article] Final-stage site-selective acylation for the total syntheses of multifidosides A-C by organocatalysis (2015)
  • Author(s): Ueda, Y.; Furuta, T.; Kawabata, T.
  • Journal Title: Angew. Chem. Int. Ed. Volume: 54 Issue: 41 Pages: 12134-12138
  • DOI: 10.1002/anie.201504729
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Total synthesis of ellagitannins through regioselective sequential functionalization of unprotected glucose (2015)
  • Author(s): H. Takeuchi, K. Mishiro, Y. Ueda, Y. Fujimori, T. Furuta, T. Kawabata
  • Journal Title: Angewandte Chemie International Edition Volume: in press Issue: 21 Pages: 6177-6180
  • DOI: 10.1002/anie.201500700
  • Peer Reviewed / Acknowledgement Compliant
• [Presentation] 鎖状1,n-ジスルホンアミドの鎖長識別モノアシル化 (2017)
  • Author(s): 橋本 悠、吉田圭佑、平田篤志、上田善弘、古田 巧、川端猛夫
  • Organizer: 日本薬学会第137年会
  • Place of Presentation: 仙台、仙台国際センター・東北大学川内地区
• [Presentation] Mechanistic Insight into Organocatalytic Enantioselective Discrimination of Axially Chiral Diamines (2016)
  • Author(s): Atsushi Hirata, Keizo Kan, Valluru Krishna Reddy, Sokeirik Yasser, Yoshihiro Ueda, Takumi Furuta, Takeo Kawabata
  • Organizer: Molecular Chirality Asia 2016
  • Place of Presentation: Knowledge Capital Congres Convention Center, Osaka
  • Int'l Joint Research
• [Presentation] 位置選択的アシル化の触媒サイクル活性化と糖類の脱酸素化への応用 (2016)
  • Author(s): 上田善弘、柳 正致、今吉亜由美、二宮 良、古田 巧、川端猛夫
  • Organizer: 第14回次世代を担う有機化学シンポジウム
  • Place of Presentation: 東京、日本薬学会長井記念ホール
• [Presentation] 最終段階位置選択的アシル化に基づく配糖体天然物の全合成 (2016)
  • Author(s): 上田善弘
  • Organizer: 第66回日本薬学会近畿支部総会・大会
  • Place of Presentation: 大阪、大阪薬科大学
  • Invited
• [Presentation] 基質認識型触媒を用いた σ-対称トリアミン誘導体の遠隔位不斉非対称化 (2016)
  • Author(s): 平田篤志、吉田圭佑、上田善弘、古田 巧、川端猛夫
  • Organizer: 第66回日本薬学会近畿支部総会・大会
  • Place of Presentation: 大阪、大阪薬科大学
• [Presentation] Short-Step Synthesis of 4-Deoxy Sugars (2016)
  • Author(s): Ryo Ninomiya, Masanori Yanagi, Yoshihiro Ueda, Takumi Furuta, Takeo Kawabata
  • Organizer: The 10th International Symposium on Integrated Synthesis
  • Place of Presentation: Awaji Yumebutai International Conference Center, Hyogo
  • Int'l Joint Research
• [Presentation] Counter-Ion-Controlled Reactivity of Acylpyridinium Ion Intermediate in Organocatalytic Site-Selective Acylation (2016)
  • Author(s): Yoshihiro Ueda, Masanori Yanagi, Ayumi Imayoshi, Takumi Furuta, Takeo Kawabata
  • Organizer: The 10th International Symposium on Integrated Synthesis
  • Place of Presentation: Awaji Yumebutai International Conference Center, Hyogo
  • Int'l Joint Research
• [Presentation] Final-Stage Site-Selective Acylation for the Total Syntheses of Multifidosides A-C by Organocatalysis (2015)
  • Author(s): Yoshihiro Ueda, Takumi Furuta, Takeo Kawabata
  • Organizer: 2015 International Chemical Congress of Pacific Basin Societies
  • Place of Presentation: Honolulu
  • Year and Date: 2015-12-19
  • Int'l Joint Research
• [Presentation] Final-Stage Site-Selective Acylation for the Total Syntheses of Multifidosides A-C (2015)
  • Author(s): Yoshihiro Ueda, Takumi Furuta, Takeo Kawabata
  • Organizer: The 13th International Kyoto Conference on New Aspects of Organic Chemistry
  • Place of Presentation: Rihga Royal Hotel Kyoto
  • Year and Date: 2015-11-10
  • Int'l Joint Research
• [Presentation] 最終段階位置選択的アシル化に基づく配糖体天然物の全合成 (2015)
  • Author(s): 上田善弘、古田 巧、川端猛夫
  • Organizer: 第６５回 日本薬学会近畿支部総会・大会
  • Place of Presentation: 大阪大谷大学
  • Year and Date: 2015-10-17
• [Presentation] Organocatalytic Site-selective Acylation of Polyol Natural Products (2015)
  • Author(s): Masanori Yanagi, Yoshihiro Ueda, Takumi Furuta, and Takeo Kawabata
  • Organizer: The 3rd International Symposium on Process Chemistry
  • Place of Presentation: Kyoto International Conference Center
  • Year and Date: 2015-07-15
  • Int'l Joint Research
• [Presentation] otal Syntheses of Multifidoside A-C: Application of Predictable Catalytic Regioselective Acylation of Glucosides at Final Stage (2015)
  • Author(s): Yoshihiro Ueda, Takumi Furuta, and Takeo Kawabata
  • Organizer: The 39th Naito Conference: The chemstry of organocatalysts
  • Place of Presentation: CATREAISE Gateaux Kingdom SAPPORO
  • Year and Date: 2015-07-08
  • Int'l Joint Research
• [Presentation] Counter-Anion-Controlled Reactivity and Selectivity in Organocatalytic Acylation of Carbohydrates (2015)
  • Author(s): Yoshihiro Ueda, Masanori Yanagi, Ayumi Tsuda, Takumi Furuta, Takeo Kawabata
  • Organizer: 第10回 有機元素セミナー
  • Place of Presentation: 京都大学 宇治キャンパス
  • Year and Date: 2015-06-08
  • Int'l Joint Research