Development of Novel Carbon-Carbon Bond-Forming Reactions under the Catalysis of Copper/NHC complexes

• Project/Area Number: 21750097
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Single-year Grants
• Research Field: Synthetic chemistry
• Research Institution: Kyoto University
• Principal Investigator: SHINTANI Ryo 京都大学, 大学院・理学研究科, 助教 (50372561)
• Project Period (FY): 2009 – 2011
• Project Status: Completed (Fiscal Year 2011)
• Budget Amount: ¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000); Fiscal Year 2011: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000); Fiscal Year 2010: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000); Fiscal Year 2009: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000)
• Keywords: 不斉合成 / 反応 / 銅 / 有機ボロン酸エステル / 含窒素複素環カルベン / 触媒的不斉合成 / 付加反応 / 置換反応 / 有機ホウ素試薬

Research Abstract

Development of Novel Carbon-Carbon Bond-Forming Reactions under the Catalysis of Copper/NHC complexes

Research Products

• [Journal Article] The Origins of Enantioselectivity in Rh-Diene Comflex Catalysed Arylation of Cyclohex-2-enones (2012)
  • Author(s): Gosiewska, S.; Raskatov, J.A.; Shintani, R.; Hayashi, T.; Brown, J.M.
  • Journal Title: Chem.Eur.J. Volume: 18 Issue: 1 Pages: 80-84
  • DOI: 10.1002/chem.201102421
  • 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): Sasaki, K.; Nishimura, T.; Sbintani, R.; Kantchev, E.A.B.; Hayashi, T.
  • Journal Title: Chem.Sci. Volume: 3 Pages: 1278-1283
  • Peer Reviewed
• [Journal Article] Copper Catalyzed Asymmetric Allylic Substitution of Allyl Phosphates with Arvl- and Alkenylboronates (2011)
  • Author(s): Ryo Shintani, Keishi Takatsu, Momotaro Takeda, Tamio Hayashi
  • Journal Title: Angewante Chemie, International Edition Volume: 50 Issue: 37 Pages: 8656-8659
  • DOI: 10.1002/anie.201103581
  • Peer Reviewed
• [Journal Article] Copper-Catalyzed 1, 4-Addition of Organoboronates to Alkylidene Cyanoacetates : Mechanistic Insight and Application to Asymmetric Catalysis (2011)
  • Author(s): 高津慶士、新谷亮、林民生
  • Journal Title: Angew. Chem Volume: 50巻 Issue: 24 Pages: 5548-5552
  • DOI: 10.1002/anie.201008196
  • Peer Reviewed
• [Journal Article] Design and Synthesis of New Chiral Phosphorus-Olefin Bidentate Ligands and Their Use in the Rhodium-Catalyzed Asymmetric Addition of Organoboroxines to N-Sulfonyl Imines (2011)
  • Author(s): Shintani, R.; Narui, R.; Tsutsumi, Y.; Hayashi, S.; Hayashi, T.
  • Journal Title: Chem.Commun. Volume: 47 Pages: 6123-6125
  • Peer Reviewed
• [Journal Article] Synthesis of Nine-Membeied Azlactones by Palladium-Catalyzed Ring-Expansim of γ-Methylidene-δ-valerolatones with Aziridines (2011)
  • Author(s): Shintani, R.; Ikehata, K.; Hayashi, T.
  • Journal Title: J.Org.Chem. Volume: 76 Issue: 11 Pages: 4776-4780
  • DOI: 10.1021/jo2006158
  • Peer Reviewed
• [Journal Article] Rhodium-Catalyzed Asymmetric Addition of Potassium Organotrifluoroborates to N-Sulfonyl Ketimines (2011)
  • Author(s): Shintani, R.; Takeda, M.; Soh, Y.-T.; Ito, T.; Hayashi, T.
  • Journal Title: Org.Lett. Volume: 13 Issue: 12 Pages: 2977-2919
  • DOI: 10.1021/ol200958q
  • Peer Reviewed
• [Journal Article] Palladium-Catalyzed Enantioselective Desymmetrization of Silacylobutanes : Construction of Silacycles Possessing a Tetraorganosilicon Stereocenter (2011)
  • Author(s): Shintani, R.; Moriya, K.; Hayashi, T.
  • Journal Title: J.Am.Chem.Soc. Volume: 133 Issue: 41 Pages: 16440-16443
  • DOI: 10.1021/ja208621x
  • Peer Reviewed
• [Journal Article] Rhodium-Catalyzed Asymmetric 1,4-Addition of Sodium Tetraarylborates to β,β-Disubstituted α,β-Unsaturated Esters (2011)
  • Author(s): Shintani, R.; Hayashi, T.
  • Journal Title: Org.Lett. Volume: 13 Pages: 350-352
  • Peer Reviewed
• [Journal Article] Guiding the nitrogen nucleophiles to the middle : palladium-catalyzed decarboxyla-tive cyclopropanation of 2-alkylidenetrimethylene carbonates with isocyanates (2011)
  • Author(s): Shintani, R.; Moriya, K.; Hayashi, T.
  • Journal Title: Chem.Commun. Volume: 47 Pages: 3057-3059
  • Peer Reviewed
• [Journal Article] Copper-Catalyzed Asymmetric Addition of Arylboronates to Isatins : A Catalytic Cycle Involving Alkoxocopper Intermediates (2010)
  • Author(s): 新谷亮、高津慶士、林民生
  • Journal Title: Chem. Commun Volume: 46巻 Issue: 36 Pages: 6822-6824
  • DOI: 10.1039/c0cc01635g
  • Peer Reviewed
• [Journal Article] Mechanistic Investigation of the Palladium-Catalyzed Decarboxylative Cyclization of γ-Methylidene-δ-valerolactones with Isocyanates : Kinetic Studies and Origin of the Site Selectivity in the Nucleophilic Attack at a (π-Allyl)palladium (2010)
  • Author(s): Shintani, R.; Tsuji, T.; Park, S.; Hayashi, T.
  • Journal Title: J.Am.Chem.Soc. Volume: 132 Pages: 7508-7513
  • Peer Reviewed
• [Journal Article] Copper-catalyzed asymmetric addition of arylboronates to isatins : a catalytic cycle involving alkoxocopper intermediates (2010)
  • Author(s): Shintani, R.; Takatsu, K.; Hayashi, T.
  • Journal Title: Chem.Commun. Volume: 46 Pages: 6822-6824
  • Peer Reviewed
• [Journal Article] Rhodium-Catalyzed Asymmetric Arylation of Azomethine Imines (2010)
  • Author(s): Shintani, R.; Soh, Y.-T.; Hayashi, T.
  • Journal Title: Org.Lett. Volume: 12 Pages: 4106-4109
  • Peer Reviewed
• [Journal Article] Rhodium-Catalyzed Asymmetric Arylation of N-Tosyl Ketimines (2010)
  • Author(s): Shintani, R.; Takeda, M.; Tsuji, T.; Hayashi, T.
  • Journal Title: J.Am.Chem.Soc. Volume: 132 Pages: 13168-13169
  • Peer Reviewed
• [Journal Article] Rhodium-Catalyzed Asymmetric Addition of Arylboronic Acids to β-Phthaliminoacrylate Esters toward the Synthesis of β-Amino Acids (2010)
  • Author(s): Nishimura, T.; Wang, J.; Nagaosa, M.; Okamoto, K.; Shintani, R.; Kwong, F.; Yu, W.; Chan, A.S.C.; Hayashi, T.
  • Journal Title: J.Am.Chem.Soc. 132 Pages: 464-465
  • Peer Reviewed
• [Journal Article] Palladium-catalyzed intramolecular decarboxylative allylic arylation of α-aryl-γ-methylidene-δ-valerolactones (2010)
  • Author(s): Shintani, R.; Tsuji, T.; Park, S.; Hayashi, T.
  • Journal Title: Chem.Commun. 46 Pages: 1697-1699
  • Peer Reviewed
• [Journal Article] Chiral Tetrafluorobenzobarrelenes as Effective Ligands for Rhodium-Catalyzed Asymmetric 1,4-Addition of Arylboroxines to β,β-Disubstituted α,β-Unsaturated Ketones (2010)
  • Author(s): Shintani, R.; Takeda, M.; Nishimura, T.; Hayashi, T.
  • Journal Title: Angew.Chem., Int.Ed. 49
  • Peer Reviewed
• [Journal Article] Rhodium/Chiral Diene-Catalyzed Asymmetric Synthesis of Spirocarbocycles : Use of Arylboron Reagents as Surrogates of 1,2-Dimetalloarenes (2010)
  • Author(s): Shintani, R.; Isobe, S.; Takeda, M.; Hayashi, T.
  • Journal Title: Angew.Chem., Int.Ed. 49
  • Peer Reviewed
• [Journal Article] Rhodium-Catalyzed Asymmetric [5+2] Cycloaddition of Alkyne-Vinylcyclopropanes (2009)
  • Author(s): Shintani, R.; Nakatsu, H.; Takatsu, K.; Hayashi, T.
  • Journal Title: Chem.Eur.J. 15 Pages: 8692-8694
  • Peer Reviewed
• [Journal Article] Stereoselective Synthesis of Spirooxindoles by Palladium-Catalyzed Decarboxylative Cyclization of γ-Methylidene-δ-valerolactones with Isatins (2009)
  • Author(s): Shintani, R.; Hayashi, S.; Murakami, M.; Takeda, M.; Hayashi, T.
  • Journal Title: Org.Lett. 11 Pages: 3754-3756
  • Peer Reviewed
• [Journal Article] Sodium Tetraarylborates as Effective Nucleophiles in Rhodium/Diene-Catalyzed 1,4-Addition to β,β-Disubstituted α,β-Unsaturated Ketones : Catalytic Asymmetric Construction of Quaternary Carbon Stereocenters (2009)
  • Author(s): Shintani, R.; Tsutsumi, Y.; Nagaosa, M.; Nishimura, T.; Hayashi, T.
  • Journal Title: J.Am.Chem.Soc. 131 Pages: 13588-13589
  • Peer Reviewed
• [Journal Article] Palladium-Catalyzed Decarboxylative [4+3] Cyclization of γ-Methylidene-δ-valerolactones with 1,1-Dicyanocyclopropanes (2009)
  • Author(s): Shintani, R.; Murakami, M.; Tsuji, T.; Tanno, H.; Hayashi, T.
  • Journal Title: Org.Lett. 11 Pages: 5642-5645
  • Peer Reviewed
• [Presentation] パラジウム触媒を用いたシラシクロブタンのエナンチオ選択的非対称化による不斉四級ケイ素中心の構築 (2012)
  • Author(s): 守屋孝平
  • Organizer: 日本化学会第92春季年会
  • Place of Presentation: 慶應義塾大学、神奈川
  • Year and Date: 2012-03-28
• [Presentation] 触媒によるリン酸アリル類の有機ボロン酸エステルを用いた不斉アリル位置換反応 (2012)
  • Author(s): 竹田桃太郎
  • Organizer: 日本化学会第92春季年会
  • Place of Presentation: 慶應義塾大学(神奈川)
  • Year and Date: 2012-03-27
• [Presentation] 遷移金属触媒による環状有機化合物の高選択的合成法の開発 (2012)
  • Author(s): 新谷亮
  • Organizer: 日本化学会第92春季年会
  • Place of Presentation: 慶應義塾大気、神奈川
  • Year and Date: 2012-03-27
• [Presentation] 銅触媒によるリン酸アリル類の有機ボロン酸エステルを用いた不斉アリル位置換反応 (2012)
  • Author(s): 竹田桃太郎
  • Organizer: 日本化学会第92春季年会
  • Place of Presentation: 慶應義塾大学、神奈川
  • Year and Date: 2012-03-27
• [Presentation] パラジウム触媒を用いたγ-メチリデン-δ-バレロラクトンとアルデヒドによる4-オキサスピロ[2.4]ヘプタンの合成 (2012)
  • Author(s): 伊藤智章
  • Organizer: 日本化学会第92春季年会
  • Place of Presentation: 慶應義塾大気、神奈川
  • Year and Date: 2012-03-26
• [Presentation] Stereoselective Synthesis of Cyclic Compounds under Palladium Catalysis (2011)
  • Author(s): R.Shintani
  • Organizer: Catalysis and Fine Chemicals 2011
  • Place of Presentation: 奈良
  • Year and Date: 2011-12-08
• [Presentation] 銅触媒を用いたアリールおよびアルケニルボロン酸エステルによるリン酸アリルの不斉アリル位置換反応 (2011)
  • Author(s): 竹田桃太郎
  • Organizer: 第58回有機金属化学討論会
  • Place of Presentation: 名古屋大学(愛知)
  • Year and Date: 2011-09-08
• [Presentation] 銅触媒を用いたアリールおよびアルケニルボロン酸エステルによるリン酸アリルの不斉アリル位置換反応 (2011)
  • Author(s): 竹田桃太郎
  • Organizer: 第58回有機金属化学討論会
  • Place of Presentation: 名古屋大学、愛知
  • Year and Date: 2011-09-08
• [Presentation] 銅触媒による有機ボロン酸エステルのアルキリデンシアノ酢酸エステルへの不斉1, 4-付加反応 (2011)
  • Author(s): 高津慶士
  • Organizer: 日本化学会第91春季年会
  • Place of Presentation: 神奈川大学(神奈川)
  • Year and Date: 2011-03-26
• [Presentation] パラジウム触媒によるγ-メチリデン-δ-バレロラクトンとイソシアネートとの脱炭酸を伴う環化反応の機構に関する研究 (2011)
  • Author(s): 新谷亮
  • Organizer: 日本化学会第91春季年会
  • 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] 銅触媒による有機ボロン酸エステルのアルキリデンシアノ酢酸エステルへの不斉1,4-付加反応 (2011)
  • Author(s): 高津慶士
  • Organizer: 日本化学会第91春季年会
  • 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] ロジウム触媒によるN-トシルケトイミンの不斉アリール化反応 (2011)
  • Author(s): 竹田桃太郎
  • Organizer: 日本化学会第91春季年会
  • 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] 新規光学活性ホスフィン-オレフィン配位子の合成とロジウム触媒による不斉1,4-付加反応への利用 (2011)
  • Author(s): 成井倫太郎
  • Organizer: 日本化学会第91春季年会
  • 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] パラジウム触媒を用いた脱炭酸を伴う2-アルキリデントリメチレンカーボネートとイソシアネートによるシクロプロパン化反応 (2011)
  • Author(s): 守屋孝平
  • Organizer: 日本化学会第91春季年会
  • 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 asymmetric construction of tetrasubstituted carbon stereocenters (2010)
  • Author(s): R.Shintani
  • Organizer: Pacifichem 2010
  • Place of Presentation: Hawaii, USA(招待講演)
  • Year and Date: 2010-12-20
• [Presentation] ロジウム触媒による不斉四置換炭素のエナンチオ選択的な構築 (2010)
  • Author(s): 新谷亮
  • 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: 2010-09-18
• [Presentation] パラジウム触媒によるγ-メチリデン-δ-バレロラクトンと1,1-ジシアノシクロプロパンとの脱炭酸を伴う[4+3]環化反応 (2010)
  • Author(s): 新谷亮
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 近畿大学本部キャンパス,東大阪
  • Year and Date: 2010-03-29
• [Presentation] テトラアリールホウ酸ナトリウムを用いたロジウム/ジエン触媒によるβ位二置換α,β-不飽和ケトンへの1,4-付加反応 (2010)
  • Author(s): 新谷亮
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 近畿大学本部キャンパス,東大阪
  • Year and Date: 2010-03-28
• [Presentation] ロジウム/キラルジエン触媒によるアリールボロキシンのβ位二置換α,β-不飽和ケトンへの不斉1,4-付加反応 (2010)
  • Author(s): 竹田桃太郎
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 近畿大学本部キャンパス,東大阪
  • Year and Date: 2010-03-28
• [Presentation] ロジウム/キラルジエン触媒によるスピロ型炭素環状化合物の不斉合成 (2010)
  • Author(s): 磯部真吾
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 近畿大学本部キャンパス,東大阪
  • Year and Date: 2010-03-28
• [Presentation] 触媒によるアリールボロン酸エステルのイサチンへの不斉付加反応 (2010)
  • Author(s): 高津慶士
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 近畿大学(大阪)
  • Year and Date: 2010-03-27
• [Presentation] 銅触媒によるアリールボロン酸エステルのイサチンへの不斉付加反応 (2010)
  • Author(s): 高津慶士
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 近畿大学本部キャンパス,東大阪
  • Year and Date: 2010-03-27
• [Presentation] γ-メチリデン-δ-バレロラクトン:パラジウム触媒による環化付加反応における新規反応剤 (2009)
  • Author(s): 新谷亮
  • Organizer: 第56回有機金属化学討論会
  • Place of Presentation: 同志社大学今出川キャンパス,京都
  • Year and Date: 2009-09-10
• [Presentation] パラジウム触媒を用いた環状化合物の新しい合成法 (2009)
  • Author(s): 新谷亮
  • Organizer: 第42回有機金属若手の会 夏の学校
  • Place of Presentation: 岐阜,十八楼
  • Year and Date: 2009-07-07
• [Presentation] γ-Methylidene-δ-valerolactones : a New Class of Reagents for the Palladium-Catalyzed Cycloaddition Reactions (2009)
  • Author(s): R.Shintani
  • Organizer: Rising Organic Chemists in CATalysis meeting
  • Place of Presentation: Muenster, Germany
  • Year and Date: 2009-06-19
• [Presentation] Rhodium-Catalyzed Asymmetric [5+2] Cycloaddition of Alkyne-Vinylcyclopropanes (2009)
  • Author(s): R.Shintani
  • Organizer: Rising Organic Chemists in CATalysis meeting
  • Place of Presentation: Muenster, Germany
  • Year and Date: 2009-06-19