Synthesis of non-biaryl compounds with axial chirality and their application to asymmetric reactions

• Project/Area Number: 26410109
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Synthetic chemistry
• Research Institution: Chiba University
• Principal Investigator: MINO TAKASHI 千葉大学, 大学院工学研究科, 准教授 (40302533)
• Project Period (FY): 2014-04-01 – 2017-03-31
• Project Status: Completed (Fiscal Year 2016)
• Budget Amount: ¥5,070,000 (Direct Cost: ¥3,900,000、Indirect Cost: ¥1,170,000); Fiscal Year 2016: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000); Fiscal Year 2015: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000); Fiscal Year 2014: ¥2,600,000 (Direct Cost: ¥2,000,000、Indirect Cost: ¥600,000)
• Keywords: 不斉反応 / 不斉配位子 / パラジウム触媒 / 軸不斉 / アミノホスフィン / キラル化合物 / 触媒的不斉反応

Outline of Final Research Achievements

In this study, we found the non-biaryl type axially chiral compounds with t-butyl group or 2-adamantyl group instead of 1-adamantyl group. These compounds have stable axial chirality at carbon-nitrogen bond. We successfully obtained the optical active compounds with high enantiomer excesses by the optical resolution of these racemic compounds using chiral HPLC. We also used them as chiral ligands for the catalytic asymmetric reactions such as palladium catalyzed asymmetric allylic alkylations of allylic esters with dialkyl maltase and indoles in good yields with good to high enantioselectivities.

Research Products

• [Journal Article] Synthesis of o-Allyloxyethynylbenzene Derivatives via Cu-Catalyzed Suzuki-Miyaura-Type Reaction and Their Transformations for Heterocyclic Compounds (2017)
  • Author(s): Kohei Watanabe, Takashi Mino, Eri Ishikawa, Miyu Okano, Tatsuya Ikematsu, asushi Yoshida, Masami Sakamoto,Kazuki Sato and Kazuhiro Yoshida
  • Journal Title: Eur. J. Org. Chem. Volume: 2017 Issue: 16 Pages: 2359-2368
  • DOI: 10.1002/ejoc.201700217
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Chiral N-adamantyl-trans-cinnamylaniline type ligands: synthesis and application to palladium-catalyzed asymmetric allylic alkylation of indoles (2016)
  • Author(s): Takashi Mino, Kenji Nishikawa, Moeko Asano, Yamato Shima, Toshibumi Ebisawa, Yasushi Yoshida, Masami Sakamoto
  • Journal Title: Organic & Biomolecular Chemistry Volume: 14 Issue: 31 Pages: 7509-7519
  • DOI: 10.1039/c6ob01354f
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] BINOL-Al Catalysed Asymmetric Cyclization and Amplification: Preparation of Optically Active Menthol Analogs (2015)
  • Author(s): Hisanori Itoh, Hironori Maeda, Shinya Yamada, Yoji Hori, Takashi Mino, Masami Sakamoto
  • Journal Title: Org. Biomol. Chem. Volume: 13 Issue: 20 Pages: 5817-5825
  • DOI: 10.1039/c5ob00433k
  • Peer Reviewed
• [Journal Article] BICMAP-rhodium(I)-catalyzed asymmetric 1,4-addition of arylboronic acids to coumarins (2015)
  • Author(s): Takashi Mino, Kazuki Miura, Hiroyuki Taguchi, Kohei Watanabe, Masami Sakamoto
  • Journal Title: Tetrahedron: Asymm. Volume: 26 Issue: 18-19 Pages: 1065-1068
  • DOI: 10.1016/j.tetasy.2015.08.005
  • Peer Reviewed
• [Journal Article] Chiral N-(tert-butyl)-N-methylaniline type ligands: Synthesis and application to palladium-catalyzed asymmetric allylic alkylation (2015)
  • Author(s): Takashi Mino, Minato Asakawa, Yamato Shima, Haruka Yamada, Fumitoshi Yagishita, Masami Sakamoto
  • Journal Title: Tetrahedron Volume: 71 Issue: 35 Pages: 5985-5993
  • DOI: 10.1016/j.tet.2015.01.027
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] 軸性キラルN-アリール環状アミンの開発と応用 (2015)
  • Author(s): 三野 孝
  • Journal Title: 化学工業 Volume: 66 Pages: 116-124
  • Acknowledgement Compliant
• [Presentation] 2-アダマンチル基を有する軸不斉アミノホスフィン配位子の合成と利用 (2017)
  • Author(s): 三野 孝・海老澤利文・吉田泰志・坂本昌巳
  • Organizer: 日本化学会第97春季年会
  • Place of Presentation: 横浜
  • Year and Date: 2017-03-17
• [Presentation] キラルアミンを不斉源とするP,オレフィン型不斉配位子の合 成とその利用 (2017)
  • Author(s): 三野 孝・養田純平・海老澤利文・斉藤 博則・田中純矢・吉田泰志・坂本昌巳
  • Organizer: 日本化学会第97春季年会
  • Place of Presentation: 横浜
  • Year and Date: 2017-03-16
• [Presentation] 複素環化合物合成を指向したo-アリロキシエチニルベンゼン誘導体の変換反応 (2016)
  • Author(s): 渡邉康平 ・三野孝 ・石川絵梨 ・岡野美優 ・ 吉田泰志 ・坂本昌巳 ・佐藤一樹 ・吉田和弘
  • Organizer: 第60回香料・テルペンおよび精油化学に関する討論会
  • Place of Presentation: 網走
  • Year and Date: 2016-10-29
• [Presentation] 2-アダマンチル基を有する軸不斉キラルアミノホスフィン配位子の合成とその応用 (2016)
  • Author(s): 海老澤 利文・三野 孝・吉田 泰志・坂本 昌巳
  • Organizer: 第63回有機金属化学討論会
  • Place of Presentation: 東京
  • Year and Date: 2016-09-16
• [Presentation] Palladium-Catalyzed Asymmetric Allylic Alkylation Using Axially Chiral Ligands with Cinnamyl Group (2016)
  • Author(s): Takashi Mino, Toshibumi Ebisawa, Moeko Asano, Yamato Shima, Yasushi Yoshida, Masami Sakamoto
  • Organizer: Molecular Chirality Asia 2016
  • Place of Presentation: 大阪
  • Year and Date: 2016-04-21
  • Int'l Joint Research
• [Presentation] シンナミル基を有する軸性キラル配位子を用いたパラジウム触媒によるマロン酸誘導体の不斉アリル位アルキル化反応 (2016)
  • Author(s): 三野 孝・島 大和・海老澤 利文・吉田 泰志・坂本 昌巳
  • Organizer: 日本化学会第96春季年会
  • Place of Presentation: 京都
  • Year and Date: 2016-03-24
• [Presentation] 2-アダマンチル基を有する軸不斉キラルアミノホスフィン配位子の合成とその応用 (2016)
  • Author(s): 三野 孝・海老澤 利文・吉田 泰志・坂本 昌巳
  • Organizer: 日本化学会第96春季年会
  • Place of Presentation: 京都
  • Year and Date: 2016-03-24
• [Presentation] Chiral N-(tert-butyl)-N-methylaniline type ligands: Synthesis and application to palladium-catalyzed asymmetric allylic alkylation (2015)
  • Author(s): Takashi Mino, Minato Asakawa, Yamato Shima, Masami Sakamoto
  • Organizer: 2015環太平洋国際化学会議
  • Place of Presentation: ホノルル（米国）
  • Year and Date: 2015-12-15
  • Int'l Joint Research
• [Presentation] Synthesis and Application of Axially Chiral Aminophosphines with t-Butyl Group (2015)
  • Author(s): Takashi Mino, Minato Asakawa, Yamato Shima, Masami Sakamoto
  • Organizer: The 13th International Kyoto Conference on New Aspects of Organic Chemistry
  • Place of Presentation: 京都
  • Year and Date: 2015-11-09
  • Int'l Joint Research
• [Presentation] シンナミル基を有する軸性キラル配位子を用いたパラジウム触媒によるインドール類の不斉アリル位アルキル化反応 (2015)
  • Author(s): 三野 孝・朝野 萌子・海老澤 利文・西川 健士・坂本 昌巳
  • Organizer: 日本化学会第95春季年会
  • Place of Presentation: 日本大学理工学部船橋キャンパス（千葉県・船橋市）
  • Year and Date: 2015-03-29
• [Presentation] シンナミル基を有する C-N 軸不斉配位子を用いたパラジウム触媒によるインドール類の不斉アリル位 アルキル化反応 (2014)
  • Author(s): 朝野 萌子・三野 孝 ・西川 健士・八木下 史敏・坂本 昌巳
  • Organizer: 第 61 回 有機金属化学討論会
  • Place of Presentation: 九州大学病院キャンパス医学部百年講堂（福岡県・福岡市）
  • Year and Date: 2014-09-25
• [Presentation] t-ブチル基を有する軸不斉キラルアミノホスフィンの合成とその応用 (2014)
  • Author(s): 三野 孝,浅川 源,山田 遥,八木下史敏,坂本昌巳
  • Organizer: Symposium on Molecular Chirality 2014
  • Place of Presentation: 仙台国際センター（宮城県・仙台市）
  • Year and Date: 2014-06-07
• [Remarks] 千葉大学工学部総合工学科共生応用化学コース精密有機化学研究室
  • URL: http://chem.tf.chiba-u.jp/gacb06/nonframe_top.html
• [Remarks] 千葉大学大学院工学研究科共生応用化学専攻精密有機化学研究室ホームページ
  • URL: http://chem.tf.chiba-u.jp/gacb06/index.html