Development ofπ-Accepting Chiral Ligands and their Application to Catalytic Asymmetric Reactions

• Project/Area Number: 22750090
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Single-year Grants
• Research Field: Synthetic chemistry
• Research Institution: Kyoto University
• Principal Investigator: NISHIMURA Takahiro 京都大学, 大学院・理学研究科, 講師 (50335197)
• Project Period (FY): 2010 – 2011
• Project Status: Completed (Fiscal Year 2011)
• Budget Amount: ¥3,510,000 (Direct Cost: ¥2,700,000、Indirect Cost: ¥810,000); Fiscal Year 2011: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000); Fiscal Year 2010: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000)
• Keywords: 不斉合成 / 反応 / 不斉配位子 / 金属触媒 / 不斉反応 / ジエン / π受容性 / ロジウム / イリジウム / コバルト / シクロプロパン化

Research Abstract

We have developed new chiral diene ligands base on tetrafluorobenzobarrelene(tfb) framework. Their rhodium complexes displayed high catalytic activity and enantioselectivity in the addition of arylboron reagents to unsaturated bonds. Iridium/chiral tfb complexes were also found to display high catalytic activity in the asymmetric 1, 6-addition of arylboroxines to dienones giving the corresponding addition products in high yields with high enantioselectivity.

Research Products

• [Journal Article] Asymmetric Synthesis of(Triaryl) methylamines byRhodium-Catalyzed Addition of Arylboroxines to Cyclic N-SulfonylKetimines (2012)
  • Author(s): Takahiro Nishimura, Akira Noishiki, Gavin Chit Tsui, Tamio Hayashi
  • Journal Title: Journal of the American Chemical Society Volume: 134 Issue: 11 Pages: 5056-5059
  • DOI: 10.1021/ja300697c
  • Peer Reviewed
• [Journal Article] Rhodium/Diene-Catalyzed Tandem 1,4-Shift/1,4-Addition of (E)-1,2-Diphenylethenylboronic Acid to Enones : Density Functional Theory Modeling and Asymmetric Catalysis (2012)
  • Author(s): K.Sasaki, et al
  • Journal Title: Chemical Science Volume: 3 Issue: 4 Pages: 1278-1283
  • DOI: 10.1039/c2sc01093c
  • Peer Reviewed
• [Journal Article] Electronic tuning ofchiral diene ligands in iridium-catalyzedasymmetric 1, 6-addition of arylboroxinestoδ-aryl-α,β,γ,δ-unsaturated ketones (2012)
  • Author(s): Takahiro Nishimura, Akira Noishiki, Tamio Hayashi
  • Journal Title: Chemical Communications Volume: 48 Issue: 7 Pages: 973-975
  • DOI: 10.1039/c2cc16973h
  • Peer Reviewed
• [Journal Article] Concise Synthesis of .BETA.,.BETA.-Diaryl Esters and Ketones from Ethynylcarbonyl Compounds by Rhodium-catalyzed Double Arylation with Arylboroxins (2011)
  • Author(s): Takahiro Nishimura, Akira Noishiki, Tamio Hayashi
  • Journal Title: Chemistry Letters Volume: 40 Issue: 11 Pages: 1285-1287
  • DOI: 10.1246/cl.2011.1285
  • NAID: 130004426096
  • ISSN: 0366-7022, 1348-0715
  • Peer Reviewed
• [Journal Article] Rhodium-catalyzed asymmetric addition of arylboroxines to β-alkoxyacrylate esters (2011)
  • Author(s): Takahiro Nishimura, Atsuyuki Kasai, Makoto Nagaosa, Tamio
  • Journal Title: Chemical Communications Volume: 47 Issue: 37 Pages: 10488-10490
  • DOI: 10.1039/c1cc14150c
  • Peer Reviewed
• [Journal Article] Cobalt-catalyzed conjugate addition of silylacetylenes to α, β-unsaturated ketones (2011)
  • Author(s): 西村貴洋, 澤野卓大, 王恵喩, 林民生
  • Journal Title: Chemical Communications Volume: 47 Issue: 36 Pages: 10142-10144
  • DOI: 10.1039/c1cc14098a
  • Peer Reviewed
• [Journal Article] Chiral Diene-PhosphineTridentate Ligands for Rhodium-Catalyzed Asymmetric Cycloisomerization of1, 6-Enynes (2011)
  • Author(s): Takahiro Nishimura, Yuko Maeda, Tamio Hayashi
  • Journal Title: Organic Letters Volume: 13 Issue: 14 Pages: 3674-3677
  • DOI: 10.1021/ol2013236
  • Peer Reviewed
• [Journal Article] Rhodium/Chiral Diene-Catalyzed Asymmetric Cyclopolymerization of Achiral 1, 8-Diynes (2011)
  • Author(s): Yoshitaka Ichikawa, Takahiro Nishimura, Tamio Hayashi
  • Journal Title: Organometallics Volume: 30 Issue: 8 Pages: 2342-2348
  • DOI: 10.1021/om200088q
  • Peer Reviewed
• [Journal Article] Rhodium-catalyzedoxidative alkynylation of acrylate esterswith propargylic alcohols (2011)
  • Author(s): Takahiro Nishimura, Makoto Nagaosa, Tamio Hayashi
  • Journal Title: Tetrahedron Letters Volume: 52 Issue: 17 Pages: 2185-2187
  • DOI: 10.1016/j.tetlet.2010.11.120
  • Peer Reviewed
• [Journal Article] Cobalt-catalyzed conjugate addition of silylacetylenes to α,β-unsaturated ketones (2011)
  • Author(s): Takahiro Nishimura, Takahiro Sawano, Keiyu Ou, Tamio Hayashi
  • Journal Title: Chemical Communications Volume: 47 Pages: 10142-10144
  • Peer Reviewed
• [Journal Article] Rhodium-catalyzed asymmetric addition of arylboroxines to β-alkoxyacrylate esters (2011)
  • Author(s): Takahiro Nishimura, Atsuyuki Kasai, Makoto Nagaosa, Tamio Hayashi
  • Journal Title: Chemical Communications Volume: 47 Pages: 10488-10490
  • Peer Reviewed
• [Journal Article] Concise Synthesis of β,β-Diaryl Esters and Ketones from Ethynylcarbonyl Compounds by Rhodium-Catalyzed Double Arylation with Arylboroxins (2011)
  • Author(s): Takahiro Nishimura, Akira Noishiki, Tamio Hayashi
  • Journal Title: Chemistry Letters Volume: 40 Pages: 1285-1287
  • NAID: 10030220372
  • Peer Reviewed
• [Journal Article] Rhodium/Chiral Diene-Catalyzed Asymmetric Cyclopolymerization of Achiral 1,8-Diynes (2011)
  • Author(s): Yoshitaka Ichikawa, Takahiro Nishimura, Tamio Hayashi
  • Journal Title: Organometallics Volume: 30 Pages: 2342-2348
  • Peer Reviewed
• [Journal Article] Rhodium-catalyzed oxidative alkynylation of acrylate esters with propargylic alcohols (2011)
  • Author(s): Takahiro Nishimura, Makoto Nagaosa, Tamio Hayashi
  • Journal Title: Tetrahedron Letters Volume: 52 Pages: 2185-2187
  • Peer Reviewed
• [Journal Article] Rhodium-Catalyzed Enantioselective1, 6-Addition of Arylboronic Acids toEnynamides : Asymmetric Synthesis ofAxially Chiral Allenylsilanes (2010)
  • Author(s): Takahiro Nishimura, Hiroki Makino, Makoto Nagaosa, Tamio Hayashi
  • Journal Title: Journal of the American Chemical Society Volume: 132 Issue: 37 Pages: 12865-12867
  • DOI: 10.1021/ja1066509
  • Peer Reviewed
• [Journal Article] Asymmetric Cyclopropanation of Alkenes with Dimethyl Diazomalonate Catalyzed by Chiral Diene-Rhodium Complexes (2010)
  • Author(s): Takahiro Nishimura, Yuko Maeda, Tamio Hayashi
  • Journal Title: Angewandte Chemie Volume: 49 Issue: 40 Pages: 7324-7327
  • DOI: 10.1002/anie.201003775
  • Peer Reviewed
• [Journal Article] Rhodium-catalyzed asymmetric conjugatealkynylation of nitroalkenes (2010)
  • Author(s): Takahiro Nishimura, Takahiro Sawano, Sumito Tokuji, Tamio Hayashi
  • Journal Title: Chemical Communications Volume: 46 Issue: 36 Pages: 6837-6839
  • DOI: 10.1039/c0cc02181d
  • Peer Reviewed
• [Journal Article] Iridium/Chiral Diene-Catalyzed Asymmetric 1, 6-Addition of Arylboroxinestoα,β,γ,δ-Unsaturated Carbonyl Compounds (2010)
  • Author(s): Takahiro Nishimura, Yuichi Yasuhara, Takahiro Sawano, Tamio Hayashi
  • Journal Title: Journal of the American Chemical Society Volume: 132 Issue: 23 Pages: 7872-7873
  • DOI: 10.1021/ja1034842
  • Peer Reviewed
• [Journal Article] Rhodium-Catalyzed Enantioselective 1,6-Addition of Arylboronic Acids to Enynamides : Asymmetric Synthesis of Axially Chiral Allenylsilanes (2010)
  • Author(s): Takahiro Nishimura, Hiroki Makino, Makoto Nagaosa, Tamio Hayashi
  • Journal Title: Journal of the American Chemical Society Volume: 132 Pages: 12865-12867
  • Peer Reviewed
• [Journal Article] Asymmetric Cyclopropanation of Alkenes with Dimethyl Diazomalonate Catalyzed by Chiral Diene-Rhodium Complexes (2010)
  • Author(s): Takahiro Nishimura, Yuko Maeda, Tamio Hayashi
  • Journal Title: Angewandte Chemie, International Edition Volume: 49 Pages: 7324-7327
  • Peer Reviewed
• [Journal Article] Rhodium-catalyzed asymmetric conjugate alkynylation of nitroalkenes (2010)
  • Author(s): Takahiro Nishimura, Takahiro Sawano, Sumito Tokuji, Tamio Hayashi
  • Journal Title: Chemical Communications Volume: 46 Pages: 6837-6839
  • Peer Reviewed
• [Journal Article] Iridium/Chiral Diene-Catalyzed Asymmetric 1,6-Addition of Arylboroxines to α,β,γ,δ-Unsaturated Carbonyl Compounds (2010)
  • Author(s): Takahiro Nishimura, Yuichi Yasuhara, Takahiro Sawano, Tamio Hayashi
  • Journal Title: Journal of the American Chemical Society Volume: 132 Pages: 7872-7873
  • Peer Reviewed
• [Presentation] Rhodium-Catalyzed Asymmetric Alkynylation of Nitroalkenes (2012)
  • Author(s): 西村貴洋・澤野卓大・林民生
  • Organizer: 第57回有機金属化学討論会
  • Place of Presentation: 中央大学(東京都)
  • Year and Date: 2012-09-16
• [Presentation] ロジウム触媒を用いたアリールボロン酸のベンゾチオフェン1, 1-ジオキシドへの不斉付加 (2012)
  • Author(s): 西村貴洋・江邉裕祐・林民生
  • Organizer: 日本化学会第92春期年会
  • Place of Presentation: 慶応義塾大学(東京都)
  • Year and Date: 2012-03-26
• [Presentation] コバルト触媒を用いたα,β-不飽和ケトンの共役アルキニル化反応 (2012)
  • Author(s): 澤野卓大・王惠瑜・西村貴洋・林民生
  • Organizer: 日本化学会第92春期年会
  • Place of Presentation: 慶応義塾大学(東京都)
  • Year and Date: 2012-03-26
• [Presentation] コバルト触媒を用いたオキサベンゾノルボルナジエンに対する不斉アルキニル化反応 (2012)
  • Author(s): 澤野卓大・王惠瑜・西村貴洋・林民生
  • Organizer: 日本化学会第92春期年会
  • Place of Presentation: 慶応義塾大学(東京都)
  • Year and Date: 2012-03-26
• [Presentation] ロジウム触媒を用いたアリールボロン酸のベンゾチオフェン1,1-ジオキシドへの不斉付加 (2012)
  • Author(s): 西村貴洋・江邉裕祐・林民生
  • Organizer: 日本化学会第92春期年会
  • Place of Presentation: 慶応義塾大学(東京都)
  • Year and Date: 2012-03-26
• [Presentation] Chiral Diene-ased Tridentate Ligands : Rhodium Catalyzed Asymmetric Cyclopropanation and Cycloisomerization (2011)
  • Author(s): 西村貴洋・前田祐子・林民生
  • Organizer: 第58回有機金属化学討論会
  • Place of Presentation: 名古屋大学(愛知県)
  • Year and Date: 2011-09-07
• [Presentation] Chiral Diene-Based Tridentate Ligands : Rhodium-Catalyzed Asymmetric Cyclopropanation and Cycloisomerization (2011)
  • Author(s): 西村貴洋・前田祐子・林民生
  • Organizer: 第58回有機金属化学討論会
  • Place of Presentation: 名古屋大学(愛知県)
  • Year and Date: 2011-09-07
• [Presentation] ロジウム-キラルジエン触媒による末端アルキンの環状エノンへの不斉共役付加反応 (2011)
  • Author(s): 西村貴洋・永長誠・林民生
  • Organizer: 日本化学会第91春期年会
  • Year and Date: 2011-03-11
• [Presentation] ロジウム触媒を用いたニトロアルケンの不斉共役アルキニル化反応 (2011)
  • Author(s): 西村貴洋・澤野卓大・林民生
  • Organizer: 日本化学会第91春期年会
  • Year and Date: 2011-03-11
• [Presentation] イリジウム/キラルジエン触媒を用いたアリールボロキシンのδ-アリール-α,β,γ,δ-不飽和カルボニル化合物への不斉1, 6付加反応 (2011)
  • Author(s): 西村貴洋・野一色彰・林民生
  • Organizer: 日本化学会第91春期年会
  • Year and Date: 2011-03-11
• [Presentation] ロジウム触媒を用いたアリールボロキシンのβ-アルコキシアクリル酸エステルへの不斉1, 4付加反応 (2011)
  • Author(s): 西村貴洋・笠井惇如・林民生
  • Organizer: 日本化学会第91春期年会
  • Year and Date: 2011-03-11
• [Presentation] ロジウム-キラルジエン触媒による末端アルキンの環状エノンへの不斉共役付加反応 (2011)
  • Author(s): 永長誠
  • Organizer: 日本化学会第91春期年会
  • Place of Presentation: (日本化学会第91春期年会(2011)講演予稿集)
  • Year and Date: 2011-03-11
• [Presentation] ロジウム触媒を用いたニトロアルケンの不斉共役アルレキニル化反応 (2011)
  • Author(s): 澤野卓大
  • Organizer: 日本化学会第91春期年会
  • Place of Presentation: (日本化学会第91春期年会(2011)講演予稿集)
  • Year and Date: 2011-03-11
• [Presentation] イリジウム/キラルレジエン触媒を用いたアリールボロキシンのδ-アリール-α,β,γ,δ-不飽和カルボニル化合物への不斉1,6付加反応 (2011)
  • Author(s): 野一色彰
  • Organizer: 日本化学会第91春期年会
  • Place of Presentation: (日本化学会第91春期年会(2011)講演予稿集)
  • Year and Date: 2011-03-11
• [Presentation] ロジウム触媒を用いたアリールボロキシンのβ-アルコキシアクリル酸エステルへの不斉1,4付加反応 (2011)
  • Author(s): 笠井惇如
  • Organizer: 日本化学会第91春期年会
  • Place of Presentation: (日本化学会第91春期年会(2011)講演予稿集)
  • Year and Date: 2011-03-11
• [Presentation] Rhodium-catalyzed asymmetricalkynylations (2010)
  • Author(s): Takahiro Nishimura, Tamio Hayashi
  • Organizer: The International Chemical Congress of Pacific Basin Societies(Pacifichem 2010)
  • Place of Presentation: ホノルル（ハワイ）
  • Year and Date: 2010-12-16
• [Presentation] Rhodium-catalyzedasymmetric conjugate alkynylation ofα,β-unsaturated aldehydes (2010)
  • Author(s): Takahiro Nishimura, Takahiro Sawano, Tamio Hayashi
  • Organizer: The International Chemical Congress of Pacific Basin Societies(Pacifichem 2010)
  • Place of Presentation: ホノルル（ハワイ）
  • Year and Date: 2010-12-16
• [Presentation] Rhodium-catalyzed asymmetric alkynylations (2010)
  • Author(s): 西村貴洋
  • Organizer: Pacifichem 2010
  • Place of Presentation: ホノルル・ハワイ・アメリカ(招待講演)
  • Year and Date: 2010-12-16
• [Presentation] Rhodium-catalyzed asymmetric conjugate alkynylation of α,β-unsaturated aldehydes (2010)
  • Author(s): 澤野卓大
  • Organizer: Pacifichem 2010
  • Place of Presentation: ホノルル・ハワイ・アメリカ
  • Year and Date: 2010-12-16
• [Presentation] Rhodium-Catalyzed Asymmetric Alkynylation of Nitroalkenes (2010)
  • Author(s): 澤野卓大
  • Organizer: 第57回有機金属化学討論会
  • Place of Presentation: 中央大学・東京
  • Year and Date: 2010-09-16
• [Presentation] Chiral Tetrafluorobenzobarrelene Ligands for Rhodium-and Iridium-Catalyzed Asymmetric Reactions (2010)
  • Author(s): Takahiro Nishimura
  • Organizer: Inaugural Conference on Molecular & Functional Catalysis(ICMFC-1)
  • Place of Presentation: シンガポール
  • Year and Date: 2010-07-13
• [Presentation] Chiral Tetrafluorobenzobarrelene Ligands for Rhodium- and Iridium-Catalyzed Asymmetric Reactions (2010)
  • Author(s): 西村貴洋
  • Organizer: Inaugural Conference on Molecular & Functional Catalysis (ICMFC-1)
  • Place of Presentation: シンガポール(招待講演)
  • Year and Date: 2010-07-13
• [Remarks]
  • URL: http://kuchem.kyoto-u.ac.jp/orgchem/Hayashi_Lab/Index.html
• [Remarks]
  • URL: http://kuchem.kyoto-u.ac.jp/orgchem/Hayash_Lab/Index.html
• [Remarks]
  • URL: http://kuchem.kyoto-u.ac.jp/orgchem/Hayash_Lab/Index.html