Development of Chiral Bronsted Acid Catalysts

• Project/Area Number: 19350026
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Organic chemistry
• Research Institution: Gakushuin University
• Principal Investigator: AKIYAMA Takahiko Gakushuin University, 理学部, 教授 (60202553)
• Project Period (FY): 2007 – 2009
• Project Status: Completed (Fiscal Year 2009)
• Budget Amount: ¥20,020,000 (Direct Cost: ¥15,400,000、Indirect Cost: ¥4,620,000); Fiscal Year 2009: ¥3,640,000 (Direct Cost: ¥2,800,000、Indirect Cost: ¥840,000); Fiscal Year 2008: ¥5,460,000 (Direct Cost: ¥4,200,000、Indirect Cost: ¥1,260,000); Fiscal Year 2007: ¥10,920,000 (Direct Cost: ¥8,400,000、Indirect Cost: ¥2,520,000)
• Keywords: 不斉合成 / 有機合成化学 / 触媒 / エナンチオ選択性 / リン酸 / キラルブレンステッド酸 / 有機触媒 / インドール / Friedel-Craftsアルキル化反応 / 速度論的光学分割 / アルドール反応 / 非対称化 / イミン / 含窒素化合物 / 量子化学計算

Research Abstract

Asymmetric reactions by means of chiral phosphoric acid derived from (R)-BINOL as chiral Bronsted acid were investigated. Transfer hydrogenation reaction was achieved by use of a novel hydrogen donor. In order to expand the scope of the chiral phosphoric acid catalyzed reactions, intramolecular aldol reaction was studied and the corresponding cyclohexenone were obtained with excellent enantioselectivities.

Research Products

• [Journal Article] Selective Activation of Enantiotopic C(sp3)-Hydrogen by Means of a Chiral Phosphoric Acid : Asymmetric Synthesis of Chiral Tetrahydroquinoline Derivatives (2011)
  • Author(s): Mori, K.; Ehara, K.; Kurihara, K.; Akiyama, T.
  • Journal Title: J.Am.Chem.Soc. 133(16) Pages: 6166-6169
• [Journal Article] Chiral Phosphoric Acid Catalyzed Enantioselective Synthesis of β-Amino-α,α-difluoro Carbonyl Compounds, 2011, 13 (7) (2011)
  • Author(s): Kashikura, W.; Mori, K.; Akiyama, T.
  • Journal Title: Org.Lett. Volume: 13 Pages: 1860-1863
  • Peer Reviewed
• [Journal Article] Chiral Bronsted Acid-Catalyzed Asymmetric Friedel-Crafts Alkylation of Indoles with α,β-Unsaturated Ketones : Short Access to Optically Active 2-and 3-Substituted Indole Derivatives (2010)
  • Author(s): Sakamoto, T.; Itoh, J.; Mori, K.; Akiyama T.
  • Journal Title: Org.Biomol.Chem. 8(23) Pages: 5448-5454
• [Journal Article] Benzothiazoline : Highly Efficient Reducing Agent for the Enantioselective Organocatalytic Transfer Hydrogenation of α-Imino Esters (2010)
  • Author(s): Zhu, C.; Akiyama, T.
  • Journal Title: Adv.Synth.Catal. 352(11-12) Pages: 1846-1850
• [Journal Article] Enantioselective Friedel-Crafts Alkylation Reaction of Indoles with Unsaturated Acyl Phosphonates Catalyzed by a Chiral Phosphoric Acid (2010)
  • Author(s): Bachu, P.; Akiyama, T.
  • Journal Title: Chem.Commun. 46(23) Pages: 4112-4114
• [Journal Article] Expeditious Synthesis of Benzopyrans via Lewis Acid Catalyzed C-H Functionalization : Remarkable Enhancement of Reactivity by Ortho-Substituent (2010)
  • Author(s): Mori, K.; Kawasaki, T.; Sueoka, S.; Akiyama, T.
  • Journal Title: Org.Lett. 12(8) Pages: 1732-1735
• [Journal Article] Enantioselective Friedel-Crafts Alkylation of Indoles, Pyrroles, and Furans with 3, 3, 3-Trifluoropyruvate Catalyzed by Chiral Phosphoric Acid (2010)
  • Author(s): Kashikura, W.; Itoh, J.; Mori, K.; Akiyama, T.
  • Journal Title: Chem.Asian J. 5(3) Pages: 470-472
• [Journal Article] Enantioselective Friedel-Crafts Alkylation Reaction of Indoles with Unsaturated Acyl Phosphonates Catalyzed by a Chiral Phosphoric Acid, Bachu, P. (2010)
  • Author(s): Bachu, P.; Akiyama, T.
  • Journal Title: Chem.Commun. Volume: 46 Pages: 4112-4114
  • Peer Reviewed
• [Journal Article] Chiral Bronsted Acid-Catalyzed Asymmetric Friedel-Crafts Alkylation of Indoles with α,β-Unsaturated Ketones : Short Access to Optically Active 2- and 3-Substituted Indole Derivatives (2010)
  • Author(s): Sakamoto, T.; Itoh, J.; Mori, K.; Akiyama, T.
  • Journal Title: Org.Biomol.Chem. Volume: 8 Pages: 5448-5454
  • Peer Reviewed
• [Journal Article] Chiral Phosphoric Acid Catalyzed Desymmetrization of meso-1, 3-Diones : Asymmetric Synthesis of Chiral Cyclohexenones (2010)
  • Author(s): Mori, K., Katoh, T., Suzuki, T., Noji, T., Yamanaka, M., Akiyama, T.
  • Journal Title: Angew.Chem.Int.Ed. 48 Pages: 9652-9654
  • Peer Reviewed
• [Journal Article] Chiral Phosphoric Acid Catalyzed Desymmetrization of meso-1, 3-Diones: Asymmetric Synthesis of Chiral Cyclohexenones (2009)
  • Author(s): Mori, K.; Katoh, T.; Suzuki, T.; Noji, T.; Yamanaka, M.; Akiyama, T.
  • Journal Title: Angew.Chem.Int.Ed. 48(51) Pages: 9652-9654
• [Journal Article] Benzothiazoline : Highly Efficient Reducing Agent for the Enantioselective Organocatalytic Transfer Hydrogenation of Ketimines (2009)
  • Author(s): Zhu, C.; Akiyama, T.
  • Journal Title: Org.Lett. 11(18) Pages: 4180-4183
• [Journal Article] Bronsted Acid-catalyzed Nazarov Cyclization of Pyrrole Derivatives by Microwave Acceleration (2009)
  • Author(s): Bachu,P.; Akiyama, T.
  • Journal Title: Bioorg.Med.Chem.Lett. 19(14) Pages: 3764-3766
• [Journal Article] Chiral Bronsted Acid Catalyzed Hydrophosphonylation of Aldimines : DFT Study on the Effect of Substituents on thePhosphoric Acid (2009)
  • Author(s): Akiyama, T.; Morita, H.; Bachu, P.; Mori, K.; Yamanaka, M.; Hirata, T.
  • Journal Title: Tetrahedron 65(26) Pages: 4950-4956
• [Journal Article] Enantioselective Mannich-type Reaction Catalyzed by a Chiral Phosphoric Acid Bearing (S)-Biphenol Backbone (2009)
  • Author(s): Akiyama, T.; Katoh, T.; Mori, K.; Kanno, K.
  • Journal Title: Synlett 10 Pages: 1664-1666
• [Journal Article] Dual Functionalization of Allene : Facile Construction of Heteropolycycles Catalyzed by Bronsted Acid (2009)
  • Author(s): Mori, K.; Sueoka, S.; Akiyama, T.
  • Journal Title: Chem.Lett. 38(6) Pages: 628-629
• [Journal Article] Concise Construction of Quinazolines via Bronsted Acid Induced C-H Activation : Further Extensions of the "tert-Amino Effect" (2009)
  • Author(s): Mori, K.; Ohshima, Y.; Ehara, K.; Akiyama, T.
  • Journal Title: Chem.Lett. 38(6) Pages: 524-525
• [Journal Article] Enantioselective Aza Darzens Reaction Catalyzed by a Chiral Phosphoric Acid (2009)
  • Author(s): Akiyama, T.; Suzuki, T.; Mori, K.
  • Journal Title: Org.Lett. 11(11) Pages: 2445-2447
• [Journal Article] Enantioselective Robinson-type Annulation Reaction Catalyzed by Chiral Phosphoric Acid (2009)
  • Author(s): Akiyama, T.; Katoh, T.; Mori, K.
  • Journal Title: Angew.Chem.Int.Ed. 48(23) Pages: 4226-4228
• [Journal Article] Enantioselective Robinson-type Annulation Reaction Catalyzed by Chiral Phosphoric Acid (2009)
  • Author(s): Akiyama, T., Katoh, T., Mori, K.
  • Journal Title: Angew.Chem.Int.Ed. 48 Pages: 4226-4228
  • Peer Reviewed
• [Journal Article] Chiral Phosphoric Acid Catalyzed Enantioselective Friedel-Crafts Alkylation of Indoles with Nitroalkenes-Cooperative Effect of MS 3A (2008)
  • Author(s): Itoh, J.; Fuchibe, K.; Akiyama, T.
  • Journal Title: Angew.Chem.Int.Ed. 47(21) Pages: 4016-4018
• [Journal Article] Preparation of β-Amino Esters by Chiral Bronsted Acid-Catalyzed Mannich-type Reaction (2008)
  • Author(s): Itoh, J.; Fuchibe, K.; Akiyama, T.
  • Journal Title: Synthesis 8 Pages: 1319-1322
• [Journal Article] Vinylogous Mannich-type Reaction Catalyzed by an Iodine-Substituted Chiral Phosphoric Acid (2008)
  • Author(s): Akiyama, T.; Honma, Y.; Itoh, J.; Fuchibe, K.
  • Journal Title: Adv.Synth.Catal. 350(3) Pages: 399-402
• [Journal Article] Vinylogous Mannich-type Reaction Catalyzed by an lodine-Substituted Chiral Phosphoric Acid (2008)
  • Author(s): Akiyama, T.
  • Journal Title: Adv. Synth. Catal. 350 Pages: 399-402
  • Peer Reviewed
• [Journal Article] Stronger Bronsted Acid (2007)
  • Author(s): Akiyama, T.
  • Journal Title: Chem.Rev. 107(12) Pages: 5744-5758
• [Journal Article] Chiral Bronsted Acid Catalyzed Enantioselective Mannich-type Reaction (2007)
  • Author(s): Yamanaka, M.; Itoh, J.; Fuchibe,K.; Akiyama, T.
  • Journal Title: J.Am.Chem.Soc. 129(21) Pages: 6756-6764
• [Journal Article] Stronger Bronsted Acid (2007)
  • Author(s): Akiyama, T.
  • Journal Title: Chem. Rev. 128 Pages: 5711-5758
  • Peer Reviewed
• [Journal Article] Chiral Bronsted Acid-catalyzed Enantioselective Mannich-type Reaction (2007)
  • Author(s): Yamanaka, M.
  • Journal Title: J. Am. Chem. Soc. 129 Pages: 972-978
  • Peer Reviewed
• [Presentation] キラルブレンステッド酸触媒を用いたインドールとα,β-不飽和ケトンとの不斉Friedel-Craftsアルキル化反応 (2011)
  • Author(s): 酒本翼・森啓二・秋山隆彦
  • Organizer: 日本化学会第91回春季年会
  • Place of Presentation: 神奈川大学
  • Year and Date: 2011-03-26
• [Presentation] キラルブレンステッド酸触媒の開発と新展開 (2011)
  • Author(s): 秋山隆彦
  • Organizer: The 2nd Symposium on Chiral Science & Technology : Mesochemistry & Chemical Wisdom
  • Place of Presentation: 早稲田大学
  • Year and Date: 2011-03-02
• [Presentation] Enantioselective Friedel-Crafts Alkylation of Indoles, Pyrroles, and Furan with Trifluoropyruvate Catalyzed by Chiral Phosphoric Acid (2010)
  • Author(s): Wataru Kashikura, Keiji Mori, Takahiko Akiyama
  • Organizer: Pacifichem2010
  • Place of Presentation: Honolulu, Hawaii, USA
  • Year and Date: 2010-12-19
• [Presentation] Chiral Bronsted Acid-catalyzed Asymmetric Friedel-Crafts Alkylation reaction of a,b-Unsaturated Ketones : Rapid Access to Optically Active 2- and 3-Substituted Indole Derivatives (2010)
  • Author(s): Tsubasa Sakamoto, Keiji Mori, Takahiko Akiyama
  • Organizer: Pacifichem2010
  • Place of Presentation: Honolulu, Hawaii, USA
  • Year and Date: 2010-12-19
• [Presentation] Recent Progress in the Chiral Phosphoric Acid Catalyzed Reactions (2010)
  • Author(s): Takahiko Akiyama
  • Organizer: Pacifichem2010
  • Place of Presentation: Honolulu, Hawaii, USA
  • Year and Date: 2010-12-17
• [Presentation] キラルブレンステッド酸触媒を用いたインドールとα,β-不飽和ケトンとの不斉Friedel-Craftsアルキル化反応 (2010)
  • Author(s): 酒本翼・伊藤淳二・森啓二・秋山隆彦
  • Organizer: 第98回有機合成シンポジウム
  • Place of Presentation: 早稲田大学
  • Year and Date: 2010-11-05
• [Presentation] キラルブレンステッド酸触媒の新展開 (2010)
  • Author(s): Takahiko Akiyama
  • Organizer: 第3回有機触媒シンポジウム
  • Place of Presentation: 東北大学
  • Year and Date: 2010-09-22
• [Presentation] Chiral Bronsted Acid-Catalyzed Asymmetric Reactions (2010)
  • Author(s): Takahiko Akiyama
  • Organizer: Gordon Conference on Organic Reactions and Processes
  • Place of Presentation: Bryant University, RI, USA
  • Year and Date: 2010-07-20
• [Presentation] Chiral Bronsted Acid-Catalyzed Asymmetric Reactions (2010)
  • Author(s): Takahiko Akiyama
  • Organizer: International Symposium on Organocatalysis
  • Place of Presentation: MacPlanck Institute, Muelheim, Germany
  • Year and Date: 2010-07-16
• [Presentation] キラルブレンステッド酸触媒を用いた不斉合成の新展開 (2010)
  • Author(s): 秋山隆彦
  • Organizer: 日本薬学会第130年会
  • Place of Presentation: 岡山大学,岡山
  • Year and Date: 2010-03-29
• [Presentation] キラルブレンステッド酸触媒を用いた不斉合成の新展開:弱い相互作用による立体制御 (2010)
  • Author(s): 秋山隆彦
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 近畿大学,東大阪
  • Year and Date: 2010-03-26
• [Presentation] Chiral Bronsted Acid-Catalyzed Asymmetric Reactions (2010)
  • Author(s): 秋山隆彦
  • Organizer: International Conference in Chemistry, Chem 06,"Contemporary Chemistry and Environment"
  • Place of Presentation: Cairo University, Cairo, Egypt. (Plenary Lecture)
  • Year and Date: 2010-03-01
• [Presentation] Chiral Bronsted Acid-Catalyzed Asymmetric Reactions (2010)
  • Author(s): 秋山隆彦
  • Organizer: 11th Florida IUPAC-Sponsored Heterocyclic & Synthetic Conference
  • Place of Presentation: University of Florida, Gainesville, Florida, USA (Invited Lecture)
• [Presentation] Chiral Bronsted Acid-Catalyzed Asymmetric Reactions (2009)
  • Author(s): 秋山隆彦
  • Organizer: International Symposium on Catalysis and Fine Chemicals 2009
  • Place of Presentation: Korea University, Seoul, Korea
  • Year and Date: 2009-12-14
• [Presentation] キラルブレンステッド酸触媒を用いた不斉合成-弱い相互作用による立体制御 (2009)
  • Author(s): 秋山隆彦
  • Organizer: 第58回有機合成化学協会関東支部シンポジウム
  • Place of Presentation: 長岡科学技術大学
  • Year and Date: 2009-11-28
• [Presentation] キラルブレンステッド酸触媒を用いた不斉合成-弱い相互作用による立体制御 (2009)
  • Author(s): 秋山隆彦
  • Organizer: プロセス化学を指向する精密合成化学シンポジウム
  • Place of Presentation: 京都テルサ
  • Year and Date: 2009-06-01
• [Presentation] キラルブレンステッド酸触媒の開発と不斉合成反応への展開 (2009)
  • Author(s): 秋山隆彦
  • Organizer: 第5回筑波大学学際物質科学研究センター機能性分子シンポジウム
  • Place of Presentation: 筑波大院数理物質科学
  • Year and Date: 2009-02-21
• [Presentation] キラルブレンステッド酸触媒を用いた含窒素化合物の不斉合成 (2009)
  • Author(s): 秋山隆彦
  • Organizer: 第14回精密合成化学セミナー
  • Place of Presentation: 北大院
  • Year and Date: 2009-01-09
• [Presentation] Chiral Bronsted Acid-Catalyzed Asymmetric Reactions (2009)
  • Author(s): 秋山隆彦
  • Organizer: The 13th Asian Chemical Congress
  • Place of Presentation: Shanghai, China
• [Presentation] キラルブレンステッド酸触媒による速度論的光学分割を利用した縮環エノンの不斉合成 (2009)
  • Author(s): 野路卓也・加藤拓也・森啓二・秋山隆彦
  • Organizer: 第58回有機合成化学協会関東支部シンポジウム
  • Place of Presentation: 長岡科学技術大学, 長岡
• [Presentation] キラルブレンステッド酸触媒を用いた含窒素化合物の不斉合成 (2008)
  • Author(s): 秋山隆彦
  • Organizer: 第23回農薬デザイン研究会
  • Place of Presentation: 大手町サンスカイルーム(東京)
  • Year and Date: 2008-11-06
• [Presentation] キラルブレンステッド酸触媒を用いた含窒素化合物の不斉合成 (2008)
  • Author(s): 秋山隆彦
  • Organizer: 有機合成化学協会関東支部ミニシンポジウム
  • Place of Presentation: 東京農工大(東京)
  • Year and Date: 2008-09-12
• [Presentation] Chiral Bronsted Acid-Catalyzed Enantioselective Synthesis of Nitrogen-containing Compounds (2008)
  • Author(s): 秋山隆彦
  • Organizer: The 9th International Symposium on Organic Reactions
  • Place of Presentation: Chiayi, Taiwan
• [Presentation] キラルブレンステッド酸触媒を用いた不斉合成反応 (2007)
  • Author(s): 秋山隆彦
  • Organizer: 日本化学会第1回関東支部大会
  • Place of Presentation: 首都大学東京
  • Year and Date: 2007-09-27
• [Presentation] Chiral Bronsted Acid-catalyzed Asymmetric Aza Diels-Alder Reactions (2007)
  • Author(s): 秋山隆彦
  • Organizer: International Symposium on Catalysis and Fine Chemicals 2007
  • Place of Presentation: Nanyang Technological University, Singapore
• [Presentation] キラルブレンステッド酸触媒を用いた不斉合成反応 (2007)
  • Author(s): 秋山隆彦
  • Organizer: 日本化学会第1回関東支部大会
  • Place of Presentation: 東京(首都大学東京)
• [Presentation] キラルブレンステッド酸触媒を用いた不斉合成 (2007)
  • Author(s): 秋山隆彦
  • Organizer: プロセス化学会サマーシンポジウム
  • Place of Presentation: 東京
• [Presentation] キラルブレンステッド酸触媒を用いた不斉合成 (2007)
  • Author(s): 秋山隆彦
  • Organizer: 前期(春季)有機合成化学講習会
  • Place of Presentation: 東京
• [Presentation] Chiral Bronsted Acid-catalyzed Asymmetric Aza Diels-Alder Reactions, 2nd International Conference on Advanced Organic Synthesis Directed toward the Ultimate Efficiency andPracticability (2007)
  • Author(s): 秋山隆彦
  • Organizer: International Conference on Asymmetric Organocatalysis
  • Place of Presentation: Ohtsu, Japan
• [Book] キラルBronsted酸触媒,進化を続ける有機触媒,丸岡啓二編 (2009)
  • Author(s): 秋山隆彦
  • Publisher: 化学同人
• [Book] Chiral Bronsted Acid, in "Acid Catalysis in Modern Organic Synthesis", Edited by H. Yamamoto, K. Ishihara, Weinheim, Germany (2008)
  • Author(s): 秋山隆彦
  • Publisher: Wiley-VCH
• [Book] キラルブレンステッド酸触媒を用いた不斉合成反応,ファインケミカル37(5) (2008)
  • Author(s): 秋山隆彦
  • Publisher: CMC出版
• [Remarks] ホームページ等
  • URL: http://www-cc.gakushuin.ac.jp/~940020/akiyama_site/
• [Remarks]
  • URL: http://www-cc.gakushuin.ac.jp/~940020/akiyama_site/index.html
• [Remarks]
  • URL: http://www-cc.gakushuin.ac.jp/~940020/akiyama_site/
• [Remarks]
  • URL: http://www-cc.gakushuin.ac.jp/~940020/akiyama_site/
• [Patent(Industrial Property Rights)] 光学活性ビフェニルリン酸誘導体 (2008)
  • Inventor(s): 菅野和明, 竹原潤, 高井正樹, 秋山隆彦
  • Industrial Property Rights Holder: 三菱化学株式会社
  • Industrial Property Number: 2008-210859
  • Filing Date: 2008-08-19