有機触媒及び遷移金属触媒を協奏的に利用した不斉プロパルギル位置換反応の開発

• Project Area: Advanced Molecular Transformations by Organocatalysts
• Project/Area Number: 26105708
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: The University of Tokyo
• Principal Investigator: 西林 仁昭 東京大学, 工学(系)研究科(研究院), 准教授 (40282579)
• Project Period (FY): 2014-04-01 – 2016-03-31
• Project Status: Discontinued (Fiscal Year 2015)
• Budget Amount: ¥7,020,000 (Direct Cost: ¥5,400,000、Indirect Cost: ¥1,620,000); Fiscal Year 2015: ¥3,510,000 (Direct Cost: ¥2,700,000、Indirect Cost: ¥810,000); Fiscal Year 2014: ¥3,510,000 (Direct Cost: ¥2,700,000、Indirect Cost: ¥810,000)
• Keywords: 協奏触媒 / 有機触媒 / 金属触媒 / エナンチオ選択的反応 / ルテニウム / リン酸

Outline of Annual Research Achievements

本研究課題では、新しい協奏的不斉合成反応の開発に関して、従来では適用出来なかった有機触媒として有効に働く光学活性リン酸誘導体を配位子部位に導入した硫黄架橋２核ルテニウム錯体を新しい設計・合成に成功し、この触媒を用いた時にのみ特異的にエナンチオ選択性が発現する触媒的プロパルギル位置換反応の開発に成功した。具体的には、有機触媒として広く用いられているキラルリン酸アミドを架橋硫黄部位に導入したハイブリッド型硫黄架橋二核ルテニウム錯体を新たに設計・合成し、このハイブリッド型触媒を用いることによる不斉プロパルギル位置換反応の開発に成功した。本反応では、プロパルギルアルコールとルテニウム錯体との反応によって生成するアレニリデン錯体に対して、配位子のリン酸アミド部位との水素結合によって制御された求核剤が求核攻撃することによって不斉が誘起されている。今回、求核剤としてアミドを用いた不斉プロパルギル位アミド化反応の開発に成功し、適用可能なアミドの置換基の種類について詳細な検討を行い、置換基効果と不斉誘起との相関関係を明らかにすることに成功した。

Research Progress Status

27年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

27年度が最終年度であるため、記入しない。

Research Products

• [Journal Article] Synthesis and Reactivity of Molybdenum-Dinitrogen Complexes Bearing PNN-Type Pincer Ligand (2015)
  • Author(s): K. Arashiba, K. Nakajima, Y. Nishibayashi
  • Journal Title: Z. Anorg. Allg. Chem. Volume: 641 Issue: 1 Pages: 100-104
  • DOI: 10.1002/zaac.201400117
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Cooperative Catalytic Reactions: Enantioselective Propargylic Alkylation of Propargylic Alcohols with Enecarbamates Using Ruthenium and Phosphoramide Hybrid Catalysts (2015)
  • Author(s): Y. Senda, K. Nakajima, Y. Nishibayashi
  • Journal Title: Angew. Chem. Int. Ed. Volume: 54 Issue: 13 Pages: 4060-4064
  • DOI: 10.1002/anie.201411601
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Radical Addition to Corannulene Mediated by Visible Light-Photoredox Catalysts (2015)
  • Author(s): Kazunari Nakajima, Yuya Ashida, Sunao Nojima, Yoshiaki Nishibayashi
  • Journal Title: Chemistry Letters Volume: 44 Issue: 4 Pages: 545-547
  • DOI: 10.1246/cl.150019
  • NAID: 130005062123
  • Peer Reviewed
• [Journal Article] Synthesis and Catalytic Activity of Molybdenum-Nitride Complexes Bearing Pincer Ligands (2015)
  • Author(s): Eriko Kinoshita, Kazuya Arashiba, Shogo Kuriyama, Aya Eizawa, Kazunari Nakajima, Yoshiaki Nishibayashi
  • Journal Title: European Journal of Inorganic Chemistry Volume: 2015 Issue: 10 Pages: 1789-1794
  • DOI: 10.1002/ejic.201500017
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Copper-Catalyzed Enantioselective Etherification of Propargylic Esters with Alcohols (2015)
  • Author(s): K. Nakajima, M. Shibata, Y. Nishibayashi
  • Journal Title: J. Am. Chem. Soc. Volume: 137 Issue: 7 Pages: 2472-2475
  • DOI: 10.1021/jacs.5b00004
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Thiolate-Bridged Dinuclear Ruthenium- and Iron-Complexes as Robust and Efficient Catalysts toward Oxidation of Molecular Dihydrogen in Protic Solvents (2015)
  • Author(s): Yuki, M.; Sakata, K.; Hirao, Y.; Nonoyama,N.; Nakajima, K.; Nishibayashi, Y.
  • Journal Title: J. Am. Chem. Soc. Volume: 137 Issue: 12 Pages: 4173-4182
  • DOI: 10.1021/jacs.5b00584
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Cobalt-Catalyzed Transformation of Molecular Dinitrogen into Silylamine under Ambient Reaction Conditions (2015)
  • Author(s): Ryuji Imayoshi, HIromasa Tanaka, Yuki Matsuo, Masahiro Yuki, Kazunari Nakajima, Kazunari Yoshizawa, Yoshiaki Nishibayashi
  • Journal Title: Chemistry - A European Journal Volume: 21 Issue: 24 Pages: 8905-8909
  • DOI: 10.1002/chem.201501088
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Catalytic Reduction of Dinitrogen into Ammonia by Use of Molybdenum-Nitride Complexes Bearing Tridentate Triphosphine as Catalysts (2015)
  • Author(s): K. Arashiba, E. Kinoshita, S. Kuriyama, A. Eizawa, K. Nakajima, H. Tanaka, K. Yoshizawa, and Y. Nishibayashi
  • Journal Title: J. Am. Chem. Soc. Volume: 137 Issue: 17 Pages: 5666-5669
  • DOI: 10.1021/jacs.5b02579
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Synthesis of Phosphabenzenes by Iron-Catalyzed [2+2+2] Cycloaddition Reaction of Diynes with Phosphaalkynes (2015)
  • Author(s): K. Nakajima, S. Takata, K. Sakata, Y. Nishibayashi
  • Journal Title: Angew. Chem. Int. Ed. Volume: 54 Issue: 26 Pages: 7597-7601
  • DOI: 10.1002/anie.201502531
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Nitrogen fixation catalyzed by ferrocene-substituted dinitrogen-bridged dimolybdenum-dinitrogen complexes: unique behavior of ferrocene moiety as redox active site (2015)
  • Author(s): S. Kuriyama, K. Arashiba, K. Nakajima, H. Tanaka, K. Yoshizawa, and Y. Nishibayashi
  • Journal Title: Chem. Sci. Volume: 6 Issue: 7 Pages: 3940-3951
  • DOI: 10.1039/c5sc00545k
  • NAID: 120005841408
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Recent Progress in Transition Metal-Catalyzed Reduction of Molecular Dinitrogen under Ambient Reaction Conditions (2015)
  • Author(s): Y. Nishibayashi
  • Journal Title: Inorg. Chem. Volume: 54 Issue: 19 Pages: 9234-9247
  • DOI: 10.1021/acs.inorgchem.5b00881
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Molybdenum-Catalyzed Reduction of Molecular Dinitrogen under Ambient Reaction Conditions (2015)
  • Author(s): Y. Nishibayashi
  • Journal Title: Comptes rendus Chimie Volume: 18 Issue: 7 Pages: 776-784
  • DOI: 10.1016/j.crci.2015.01.014
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] 温和な反応条件下での遷移金属窒素錯体を分子触媒として用いた窒素分子からのアンモニア合成反応の開発 (2015)
  • Author(s): 西林仁昭
  • Journal Title: 触媒 Volume: 57 Pages: 33-38
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Enantioselective Intramolecular Propargylic Amination Using Chiral Copper-Pybox Catalyst (2014)
  • Author(s): M. Shibata, K. Nakajima, and Y. Nishibayashi
  • Journal Title: Chem. Commun. Volume: 50 Issue: 58 Pages: 7874-7877
  • DOI: 10.1039/c4cc01676a
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Synthesis and Redox Properties of PNP Pincer Complexes Based on N-Methyl-4,4'-Bipyridinium (2014)
  • Author(s): Y. Miyake, K. Nakajima, Y. Higuchi, and Y. Nishibayashi
  • Journal Title: Eur. J. Inorg. Chem. Volume: 2014 Issue: 26 Pages: 4273-4280
  • DOI: 10.1002/ejic.201402349
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Catalytic Formation of Ammonia from Molecular Dinitrogen by Use of Dinitrogen-Bridged Dimolybdenum-Dinitrogen Complexes Bearing PNP-Pincer Ligands: Remarkable Effect of Substituent at PNP-Pincer Ligand (2014)
  • Author(s): Shogo Kuriyama, Kazuya Arashiba, Kazunari Nakajima, Hiromasa Tanaka, Nobuaki Kamaru, Kazunari Yoshizawa, Yoshiaki Nishibayashi
  • Journal Title: Journal of the American Chemical Society Volume: 136 Issue: 27 Pages: 9719-9731
  • DOI: 10.1021/ja5044243
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Copper-Catalyzed Nucleophilic Trifluoromethylation of Benzylic Chlorides (2014)
  • Author(s): Y. Miyake, S. Ota, M. Shibata, K. Nakajima, and Y. Nishibayashi
  • Journal Title: Org. Biomol. Chem. Volume: 12 Issue: 30 Pages: 5594-5596
  • DOI: 10.1039/c4ob00957f
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Synthesis of Nitrogen Heterocycles via a-Aminoalkyl Radicals Generated from a-Silyl Secondary-Amines under Visible Light Irradiation (2014)
  • Author(s): K. Nakajima, M. Kitagawa, Y. Ashida, Y. Miyake, and Y. Nishibayashi
  • Journal Title: Chem. Commun. Volume: 50 Issue: 64 Pages: 8900-8903
  • DOI: 10.1039/c4cc03000a
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Cleavage and Formation of Molecular Dinitrogen in a Single System Assisted by Molybudenum Complexes Bearing Ferrocenyldiphosphine (2014)
  • Author(s): T. Miyazaki, H. Tanaka, Y. Tanabe, M. Yuki, K. Nakajima, K. Yoshizawa, and Y. Nishibayashi
  • Journal Title: Angew. Chem. Int. Ed. Volume: 53 Issue: 43 Pages: 11488-11492
  • DOI: 10.1002/anie.201405673
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Synthesis and Reactivity of Ruthenium Complexes Bearing Arsenic-Containing Arsenic-Nitrogen-Arsenic-Type Pincer Ligand (2014)
  • Author(s): Yoshiaki Tanabe, Shogo Kuriyama, Kazuya Arashiba, Kazunari Nakajima, Yoshiaki Nishibayashi
  • Journal Title: Organometallics Volume: 33 Issue: 19 Pages: 5295-5300
  • DOI: 10.1021/om5006116
  • Peer Reviewed
• [Presentation] ハーバー・ボッシュ法を超えるアンモニア合成法への挑戦 (2015)
  • Author(s): 西林仁昭
  • Organizer: 平成27年錯体化学若手の会関東支部後期勉強会
  • Place of Presentation: 東京大学
  • Year and Date: 2015-06-13
  • Invited
• [Presentation] 光学活性リン酸アミド部位を有するルテニウム錯体を用いた不斉プロパルギル位置換反応の開発 (2015)
  • Author(s): 千田泰史、中島一成、西林仁昭
  • Organizer: 日本化学会第95春季年会
  • Place of Presentation: 船橋市、日本大学 理工学部船橋キャンパス
  • Year and Date: 2015-03-26 – 2015-03-29
• [Presentation] プロパルギルエステルとインドールを用いたプロパルギル位置換反応に基づく不斉4 級炭素構築反応の開発 (2015)
  • Author(s): 土田耕平、千田泰史、中島一成、西林仁昭
  • Organizer: 日本化学会第95春季年会
  • Place of Presentation: 船橋市、日本大学 理工学部船橋キャンパス
  • Year and Date: 2015-03-26 – 2015-03-29
• [Presentation] ハーバー・ボッシュ法を超えるアンモニア合成は誕生するのか？―化石燃料に代わる次世代エネルギー源としての期待 (2014)
  • Author(s): 西林仁昭
  • Organizer: 平成26年度「実践的化学知セミナー」講演会
  • Place of Presentation: 東京都新宿区、早稲田大学
  • Year and Date: 2014-12-12
  • Invited
• [Presentation] Enantioselective Propargylic Substitution Reactions Using Ruthenium Complexes Bearing Chiral Phosphoric Amide Moiety (2014)
  • Author(s): Yasushi, Senda, Kazunari Nakajima, and Yoshiaki Nishibayashi
  • Organizer: 第2回 国際会議(兼)第7回 有機触媒シンポジウム
  • Place of Presentation: 東京都文京区、東京大学・伊藤国際学術研究センター
  • Year and Date: 2014-11-21 – 2014-11-22
• [Presentation] olybdenum-Catalyzed Reduction of Molecular Dinitrogen into Ammonia under Ambient Conditions (2014)
  • Author(s): Yoshiaki Nishibayashi
  • Organizer: The 2nd International Conference on Organometallics and Catalysis
  • Place of Presentation: 奈良市、東大寺総合文化センター
  • Year and Date: 2014-10-27 – 2014-10-29
  • Invited
• [Presentation] olybdenum-Catalyzed Reduction of Molecular Dinitrogen into Ammonia under Ambient Conditions (2014)
  • Author(s): Yoshiaki Nishibayashi
  • Organizer: The JSPS Strasbourg Symposium
  • Place of Presentation: France、Strasbourg
  • Year and Date: 2014-10-17
  • Invited
• [Presentation] ハーバー・ボッシュ法を超えるアンモニア合成法への挑戦 (2014)
  • Author(s): 西林仁昭
  • Organizer: 機能性錯体化学研究会平成26年度講演会
  • Place of Presentation: 東京都目黒区、東京大学
  • Year and Date: 2014-08-05
  • Invited
• [Presentation] Molybdenum-Catalyzed Reduction of Molecular Dinitrogen into Ammonia under Mild Reaction Conditions (2014)
  • Author(s): Yoshiaki Nishibayashi
  • Organizer: 41st International Conference on Coordination Chemistry
  • Place of Presentation: Singapore、Suntec City
  • Year and Date: 2014-07-21 – 2014-07-25
  • Invited
• [Presentation] Molybdenum-Catalyzed Reduction of Molecular Dinitrogen into Ammonia under Mild Reaction Conditions (2014)
  • Author(s): Yoshiaki Nishibayashi
  • Organizer: The 26th International Conference on Organometallic Chemistry
  • Place of Presentation: 札幌市、ロイトン札幌、北海道
  • Year and Date: 2014-07-14
  • Invited
• [Presentation] 光学活性リン酸アミド部位を有するルテニウム錯体を用いた不斉プロパルギル位置換反応の開発 (2014)
  • Author(s): 千田泰史、中島一成、西林仁昭
  • Organizer: 「有機分子触媒による未来型分子変換」第4回公開シンポジウム(分子活性化 - 有機分子触媒合同シンポジウム)
  • Place of Presentation: 札幌市、北海道大学学術交流会館
  • Year and Date: 2014-06-20 – 2014-06-21
• [Remarks] 東京大学 大学院工学系研究科 総合研究機構 西林研究室
  • URL: http://park.itc.u-tokyo.ac.jp/nishiba/