Advanced Control of Stereoselectivity and Chemoselectivity Through Supramolecular Chemistry

2010 Fiscal Year Final Research Report

• Project/Area Number: 20200053
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research a proposed research project)
• Allocation Type: Single-year Grants
• Research Field: Synthetic chemistry; Chemical pharmacy
• Research Institution: 公益財団法人微生物化学研究会・微生物化学研究所 (2010); The University of Tokyo (2008-2009)
• Principal Investigator: KUMAGAI Naoya 公益財団法人微生物化学研究会・微生物化学研究所, 有機合成研究部, 主任研究員 (40431887)
• Project Period (FY): 2008 – 2010
• Keywords: 触媒設計・反応 / 不斉合成 / 動的構造多様性触媒

Research Abstract

Advanced asymmetric catalysts exhibiting trigger-responsive property and self-assembly capability were developed based on structurally flexible amide-based ligands. These smart catalysts allowed us to link the structural dynamics and functional diversity in asymmetric catalysis.

Research Products

• [Journal Article] Asymmetric Synthesis of Isothiazole Entities Through Cu Catalysis : Direct Catalytic Asymmetric Conjugate Addition of Allyl Cyanide to α,β-Unsaturated Thioamides (2011)
  • Author(s): Yuka Yanagida, Ryo Yazaki, Naoya Kumagai, Masakatsu Shibasaki
  • Journal Title: Angew.Chem., Int.Ed. in press
  • Peer Reviewed
• [Journal Article] La/Ag Heterobimetallic Catalysis : Catalytic Asymmetric Conia-ene Reaction (2011)
  • Author(s): Akinobu Matsuzawa, Tomoyuki Mashiko, Naoya Kumagai, Masakatsu Shibasaki
  • Journal Title: Angew. Chem., Int.Ed. in press
  • Peer Reviewed
• [Journal Article] A Simplified Catalytic System for Direct Catalytic Asymmetric Aldol Reaction of Thioamides; Application to an Enantioselective Synthesis of Atorvastatin (2011)
  • Author(s): Yuji Kawato, Mitsutaka Iwata, Ryo Yazaki, Naoya Kumagai, Masakatsu Shibasaki
  • Journal Title: Tetrahedron in press
  • Peer Reviewed
• [Journal Article] Direct Catalytic Enantio-and Diastereoselective Aldol Reaction of Thioamides (2011)
  • Author(s): Mitsutaka Iwata, Ryo Yazaki, I-Hon Chen, Devarajulu Sureshkumar, Naoya Kumagai, Masakatsu Shibasaki
  • Journal Title: J.Am.Chem.Soc. 133(14) Pages: 5554-5560
  • Peer Reviewed
• [Journal Article] Cooperative Activation of Alkyne and Thioamide Functionalities; Direct Catalytic Asymmetric Conjugate Addition of Terminal Alkynes to α,β-Unsaturated Thioamides (2011)
  • Author(s): Ryo Yazaki, Naoya Kumagai, Masakatsu Shibasaki
  • Journal Title: Chem.Asian J. in press
  • Peer Reviewed
• [Journal Article] Enantioselective Synthesis of a GPR40 Agonist AMG 837 via inal Alkyne to α,β-Unsaturated Thioamide (2011)
  • Author(s): Ryo Yazaki, Naoya Kumagai, Masakatsu Shibasaki
  • Journal Title: Org.Lett. 13(5) Pages: 952-955
  • Peer Reviewed
• [Journal Article] Catalytic Asymmetric Hydroxylation of α-Alkoxycarbonyl Amides with a Pr(OiPr)3 /Amide-Based Ligand Catalyst (2011)
  • Author(s): Sho Takechi, Naoya Kumagai, Masakatsu Shibasaki
  • Journal Title: Tetrahedron Lett. 52(17) Pages: 2140-2143
  • Peer Reviewed
• [Journal Article] Catalytic Asymmetric Amination of N-Nonsubstituted α-Alkoxycarbonyl Amides : Concise Enantioselective Total Synthesis of Mycestericin F and G (2011)
  • Author(s): Farouk Berhal, Sho Takechi, Naoya Kumagai, Masakatsu Shibasaki
  • Journal Title: Chem.Eur.J. 17(6) Pages: 1915-1921
  • Peer Reviewed
• [Journal Article] Direct Catalytic Asymmetric Conjugate Addition of Terminal Alkynes to α,β-Unsaturated Thioamides (2010)
  • Author(s): Ryo Yazaki, Naoya Kumagai, Masakatsu Shibasaki
  • Journal Title: J.Am.Chem.Soc. 132(30) Pages: 10275-10277
  • Peer Reviewed
• [Journal Article] Direct Catalytic Asymmetric Aldol Reaction of Thioamides : A Concise Asymmetric Synthesis of (R)-Fluoxetine (2010)
  • Author(s): Mitsutaka Iwata, Ryo Yazaki, Naoya Kumagai, Masakatsu Shibasaki
  • Journal Title: Tetrahedron : Asymmetry 21(13-14) Pages: 1688-1694
  • Peer Reviewed
• [Journal Article] Solvent-Dependent Self-Discrimination of Bis(2-hydroxyphenyl)diamides (2010)
  • Author(s): Akinobu Matsuzawa, Akihiro Nojiri, Naoya Kumagai, Masakatsu Shibasaki
  • Journal Title: Chem.Eur.J. 16(17) Pages: 5036-5042
  • Peer Reviewed
• [Journal Article] Direct Catalytic Asymmetric Addition of Allyl Cyanide to Ketones via Soft-Lewis Acid/Hard Bronsted Base/Hard Lewis Base Cooperative Catalysis (2010)
  • Author(s): Ryo Yazaki, Naoya Kumagai, Masakatsu Shibasaki
  • Journal Title: J.Am.Chem.Soc. 132(15) Pages: 5522-5531
  • Peer Reviewed
• [Journal Article] Catalytic Asymmetric Conjugate Addition of α-Cyanoketones For the Construction of a Quaternary Stereogenic Center (2010)
  • Author(s): Yuji Kawato, Noriko Takahashi, Naoya Kumagai, Masakatsu Shibasaki
  • Journal Title: Org.Lett. 12(7) Pages: 1484-1487
  • Peer Reviewed
• [Journal Article] Catalytic Asymmetric Nitro-Mannich Reactions with a Yb/K Heterobimetallic Catalyst (2010)
  • Author(s): Tatsuya Nitabaru, Naoya Kumagai, Masakatsu Shibasaki
  • Journal Title: Molecules 15(3) Pages: 1280-1290
  • Peer Reviewed
• [Journal Article] Direct Catalytic Asymmetric Aldol Reactions of Thioamides : Toward a Stereocontrolled Synthesis of 1,3-Polyols (2009)
  • Author(s): Mitsutaka Iwata, Ryo Yazaki, Yuta Suzuki, Naoya Kumagai, Masakatsu Shibasaki
  • Journal Title: J.Am.Chem.Soc. 131(51) Pages: 18244-18245
  • Peer Reviewed
• [Journal Article] Managing Highly Coordinative Substrates in Asymmetric Catalysis : a Catalytic Asymmetric Amination with a Lanthanum-based Ternary Catalyst (2009)
  • Author(s): Tomoyuki Mashiko, Naoya Kumagai, Masakatsu Shibasaki
  • Journal Title: J.Am.Chem.Soc. 131(41) Pages: 14990-14999
  • Peer Reviewed
• [Journal Article] anti-Selective Catalytic Asymmetric Nitroaldol Reaction via a Heterobimetallic Heterogeneous Catalyst (2009)
  • Author(s): Tatsuya Nitabaru, Akihiro Nojiri, Makoto Kobayashi, Naoya Kumagai, Masakatsu Shibasaki
  • Journal Title: J.Am.Chem.Soc. 131(38) Pages: 13860-13869
  • Peer Reviewed
• [Journal Article] Direct Catalytic Asymmetric Mannich-type Reaction of Thioamides (2009)
  • Author(s): Yuta Suzuki, Ryo Yazaki, Naoya Kumagai, Msakatsu Shibasaki
  • Journal Title: Angew.Chem., Int.Ed. 48(27) Pages: 5026-5029
  • Peer Reviewed
• [Journal Article] Linking Structural Dynamics and Functional Diversity in Asymmetric Catalysis (2009)
  • Author(s): Akihiro Nojiri, Naoya Kumagai, Masakatsu Shibasaki
  • Journal Title: J.Am.Chem.Soc. 131(10) Pages: 3779-3784
  • Peer Reviewed
• [Journal Article] Direct Catalytic Asymmetric Addition of Allyl Cyanide to Ketones (2009)
  • Author(s): Ryo Yazaki, Naoya Kumagai, Masakatsu Shibasaki
  • Journal Title: J.Am.Chem.Soc. 131(9) Pages: 3195-3197
  • Peer Reviewed
• [Journal Article] Direct Catalytic Asymmetric Addition of Allylic Cyanides to Ketoimines (2008)
  • Author(s): Ryo Yazaki, Tatsuya Nitabaru, Naoya Kumagai, Masakatsu Shibasaki
  • Journal Title: J.Am.Chem.Soc. 130(44) Pages: 14477-14479
  • Peer Reviewed
• [Journal Article] An Improved Lanthanum Catalytic System for Asymmetric Amination; Toward a Practical Asymmetric Synthesis of AS-3201 (Ranirestat) (2008)
  • Author(s): Tomoyuki Mashiko, Naoya Kumagai, Masakatsu Shibasaki
  • Journal Title: Org.Lett. 10(13) Pages: 2725-2728
  • Peer Reviewed
• [Journal Article] Asymmetric Catalysis via Dynamic ustrate/Ligand Rare Earth Metal Conglomerate (2008)
  • Author(s): Akihiro Nojiri, Naoya Kumagai, Masakatsu Shibasaki
  • Journal Title: J.Am.Chem.Soc. 130(17) Pages: 5630-5631
  • Peer Reviewed
• [Presentation] University of Colorado (2010)
  • Organizer: Soft Lewis Acid/Hard Bronsted Base Cooperative Catalysis for the Construction of Tetrasubstituted Stereogenic Centers
  • Place of Presentation: 依頼講演コロラド大学,アメリカ
  • Year and Date: 2010-08-09
• [Presentation] Tampere University of Technology (2010)
  • Organizer: Recent Progress in Asymmetric C.C Bond formation via Proton Transfer
  • Place of Presentation: 依頼講演Tampere University of Technology,フィンランド
  • Year and Date: 2010-07-19
• [Presentation] RSC-CSJ Joint Symposium. (2010)
  • Organizer: Atom-economical Catalytic Asymmetric Reactions and Their Application to Efficient Synthesis of Therapeutics
  • Place of Presentation: Chemistry for a Sustainable World RSC Burlington House,ロンドン,イギリス
  • Year and Date: 2010-07-16
• [Presentation] BIT's 1st Annual World Congress in Catalytic Asymmetric Synthesis北京コンベンションセンター (2010)
  • Organizer: Rare Earth Metal/Amide-Based Ligand Complexes : Structural Dynamics, Functional Diversity, and Asymmetric Catalysis
  • Place of Presentation: 北京,中国
  • Year and Date: 2010-05-21
• [Presentation] 日本薬学会 (2010)
  • Organizer: 高原子効率的な触媒的不斉反応の開発と医薬品の効率的合成への応用
  • Place of Presentation: 岡山コンベンションセンター
  • Year and Date: 2010-03-28
• [Book] Phospholane,1,1_-(1,2-Ethanediyl)-bis[2,5-diphenyl- (2S,2S_,5S,5S_)1 and Phospholane, 1,1-(1,2-Ethanediyl)-bis[2,5-diphenyl-(2R,2R_,5R,5R_)" ,Encyclopedia of Reagents for Organic Synthesis (2010)
  • Author(s): Naoya Kumagai
• [Book] e-EROS (1,2-Bis((2R,5R)-2,5-Diisopropylphospholan-1-yl)benzene1 and 1,2-Bis((2S,5S)-2,5-diisopropylphospholan-1-yl)benzene), Wiley-VCH (2009)
  • Author(s): Naoya Kumagai
  • Total Pages: 11
• [Remarks] ホームページ等
  • URL: http://www.bikaken.or.jp/research/group/shibasaki/shibasaki-lab/index.html
• [Patent(Industrial Property Rights)] チオアミド化合物、チオアミド化合物の製造方法、[(4R,6R)-6-アミノエチル-1,3-ジオキサン-4-イル]アセテート誘導体の製造方法、及びアトルバスタチンの製造方法 (2011)
  • Inventor(s): 熊谷直哉, 柴崎正勝
  • Industrial Property Rights Holder: 微生物化学研究会
  • Industrial Property Number: 特許出願,2011-035006
  • Filing Date: 2011-02-21
• [Patent(Industrial Property Rights)] 立体選択的不斉ニトロアルドール反応用触媒 (2010)
  • Inventor(s): 二田原達也, 熊谷直哉, 柴崎正勝
  • Industrial Property Rights Holder: 東京大学
  • Industrial Property Number: PCT/JP2010/000387
  • Filing Date: 2010-01-25
  • Overseas
• [Patent(Industrial Property Rights)] 立体選択的不斉ニトロアルドール反応用触媒 (2009)
  • Inventor(s): 二田原達也, 熊谷直哉, 柴崎正勝
  • Industrial Property Rights Holder: 東京大学
  • Industrial Property Number: 特許出願2009-01394,2009-01394
  • Filing Date: 2009-01-26