Design of chiral calix arene for synthesis of optically-active unnatural amino acids by asymmetric complexation

• Project/Area Number: 23750037
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Multi-year Fund
• Research Field: Organic chemistry
• Research Institution: Niigata University
• Principal Investigator: TAYAMA Eiji 新潟大学, 自然科学系, 准教授 (90372474)
• Project Period (FY): 2011 – 2013
• Project Status: Completed (Fiscal Year 2013)
• Budget Amount: ¥4,550,000 (Direct Cost: ¥3,500,000、Indirect Cost: ¥1,050,000); Fiscal Year 2013: ¥650,000 (Direct Cost: ¥500,000、Indirect Cost: ¥150,000); Fiscal Year 2012: ¥650,000 (Direct Cost: ¥500,000、Indirect Cost: ¥150,000); Fiscal Year 2011: ¥3,250,000 (Direct Cost: ¥2,500,000、Indirect Cost: ¥750,000)
• Keywords: 不斉包接 / 転位反応 / 四級アンモニウム塩 / アミノ酸 / 不斉合成 / 有機触媒 / 光学活性 / 包接

Research Abstract

Optically-active large cyclic compounds were prepared from calix arenes. NMR analysis of a 1:1 complex between the chiral calix arene and a racemic tetraalkylamkmonium salt was examined. Each enantiomer of the tetraalkylammonium salt were observed separately in the spectrum. Asymmetric rearrangements of the tetraalkylammonium salts using the chiral calix arenes as an organo-catalyst were examined. The rearrangement products were successfully converted to the corresponding unnatural amino acids.

Research Products

• [Journal Article] 第四級アンモニウムイリドを中間体とする塩基促進型 Sommelet-Hauser 転位の新しい展開 (2014)
  • Author(s): 田山 英治
  • Journal Title: 有機合成化学協会誌 Volume: Vol. 72 Pages: 418-428
  • NAID: 130004548592
  • Peer Reviewed
• [Journal Article] 第四級アンモニウムイリドを中間体とする塩基促進型Sommelet-Hauser転位の新しい展開 (2014)
  • Author(s): 田山英治
  • Journal Title: 有機合成化学協会誌 Volume: 72 Pages: 418-428
  • NAID: 130004548592
  • Peer Reviewed
• [Journal Article] A unique and simple preparative method for α-arylpipecolinic acid esters via base-induced Sommelet-Hauser rearrangement (2013)
  • Author(s): 田山 英治, 佐藤 亮太, 伊藤 統, 岩本啓, 長谷川 英悦
  • Journal Title: Heterocycles Volume: Vol. 87 Pages: 381-388
  • NAID: 120006748858
  • Peer Reviewed
• [Journal Article] A unique and simple preparative method for α-arylpipecolinic acid esters via base-induced Sommelet-Hauser rearrangement (2013)
  • Author(s): Eiji Tayama, Ryota Sato, Motoshi Ito, Hajime Iwamoto, and Eietsu Hasegawa
  • Journal Title: Heterocycles Volume: 87 Issue: 2 Pages: 381-388
  • DOI: 10.3987/com-12-12619
  • NAID: 120006748858
  • Peer Reviewed
• [Journal Article] A formal method for the de-N,N-dialkylation of Sommelet-Hauser rearrangement products (2012)
  • Author(s): 田山 英治, 佐藤 亮太, 竹立 圭佑, 岩本 啓, 長谷川 英悦
  • Journal Title: Tetrahedron Volume: Vol. 68 Pages: 4710-4718
  • NAID: 120006746914
  • Peer Reviewed
• [Journal Article] 1,2-Dimethoxy-4,5-dimethylene : a new protecting group for acyclic amino acid derivatives prepared by Stevens rearrangement (2012)
  • Author(s): 田山 英治, 竹立 圭佑, 岩本 啓, 長谷川 英悦
  • Journal Title: Tetrahedron Lett Volume: Vol. 53 Pages: 1373-1375
  • NAID: 120006746916
  • Peer Reviewed
• [Journal Article] A formal method for the de-N,N-dialkylation of Sommelet-Hauser rearrangement products (2012)
  • Author(s): Eiji Tayama, Ryota Sato, Keisuke Takedachi, Hajime Iwamoto, Eietsu Hasegawa
  • Journal Title: Tetrahedron Volume: 68 Issue: 24 Pages: 4710-4718
  • DOI: 10.1016/j.tet.2012.04.015
  • NAID: 120006746914
  • Peer Reviewed
• [Journal Article] 1,2-Dimethoxy-4,5-dimethylene: a new protecting group for acyclic amino acid derivatives prepared by Stevens rearrangement (2012)
  • Author(s): Eiji Tayama, Keisuke Takedachi, Hajime Iwamoto, Eietsu Hasegawa
  • Journal Title: Tetrahedron Letters Volume: 53 Issue: 11 Pages: 1373-1375
  • DOI: 10.1016/j.tetlet.2012.01.013
  • NAID: 120006746916
  • Peer Reviewed
• [Presentation] Sommelet-Hauser 転位を経由するα-アリールピペコリン酸誘導体の合成 (2012)
  • Author(s): 伊藤 統, 佐藤 亮太, 田山 英治
  • Organizer: 第64回有機合成化学協会関東支部シンポジウム
  • Place of Presentation: 長岡技術科学大学
• [Presentation] Sommelet-Hauser転位を経由するα-アリールピペコリン酸誘導体の合成 (2012)
  • Author(s): 伊藤 統、佐藤 亮太、田山 英治
  • Organizer: 第64回（2012）有機合成化学協会関東支部シンポジウム(新潟シンポジウム)
  • Place of Presentation: 長岡技術科学大学
• [Presentation] Sommelet-Hauser 転位を経由するα-アリール-α-ハロ酢酸エステルの合成と応用 (2011)
  • Author(s): 佐藤 亮太, 田山 英治
  • Organizer: 第62回有機合成化学協会関東支部シンポジウム
  • Place of Presentation: 新潟大学工学部