Synthesis of Optically Active Compounds Having Pentafluorophenyl Group - The Structure and Function

1999 Fiscal Year Final Research Report Summary

• Project/Area Number: 10555321
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 展開研究
• Research Field: Synthetic chemistry
• Research Institution: Okayama University
• Principal Investigator: UTAKA Masanori Okayama University, Faculty of Engineering, Professor, 工学部, 教授 (30033153)
• Co-Investigator(Kenkyū-buntansha): MINAI Masayoshi Sumitomo Chemical Co., Institute of Organic Synthesis, Group Manager, 有機合成研究所, 主任研究員 ; EMA Tadashi Okayama University, The Graduate School of Natural Science and Technology, Research Associate, 大学院・自然科学研究科, 助手 (20263626) ; SAKAI Takashi Okayama University, Faculty of Engineering, Professor, 工学部, 教授 (00170556)
• Project Period (FY): 1998 – 1999
• Keywords: fluorine / optically active / diol / amino alcohol / lipase

Research Abstract

Pentafluorophenyl group shows both electron-withdrawing property and stucking ability for electron-rich aromatic molecules. However, there is few report on its application to functional materials. We expected that chiral pentafluorophenyl group-containing compounds will be useful for liquid crystals and molecular recognition materials.
The lipase LIP-catalyzed kinetic resolution of 2-hydroxy-2-(pentafluorophenyl)acetonitrile (1) at 0℃ afforded optically active (R)-1 with 96% ee and its (S)-acetate derivative with 98% ee. Subsequently, we successfully converted (R)-1 to (1R, 2R)-bis(pentafluorophenyl)ethane-1, 2-diol ((1R, 2R)-(2)) with 94% ee and (S)-1 to (1S, 2S)-2 with 87% ee. We found that the addition of TMSCI accelerated the NaBHィイD24ィエD2 reduction of the imine intermediate and simultaneously suppressed the racemization. We also synthesized optically active diols and amino alcohols such as 1-(pentafluorophenyl)-2-phenylethane-1, 2-diol, 2-amino-1, 2-bis(pentafluorophenyl)ethanol, and 2-amino-1-(pentafluorophenyl)-2-phenylethanol according to the similar method. Furthermore, we confirmed the stucking interaction between the pentafluorophenyl group and electron-rich aromatic groups by means of the X-ray crystal structure analysis and NMR measurements.

Research Products

• [Publications] Takashi Sakai: "Lipase-Catalyzed Transesterification of 2-Hydroxy-2-(pentafluorophenyl)acetonitrile Leading to (1R,2R)- and (1S,2S)-Bis(pentafluorophenyle)ethane-1,2-diol"The Journal of Organic Chemistry. (印刷中).
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Takashi Sakai et al.: "Lipase-Catalyzed Transesterification of 2-hydroxy-2-(pentafluorophenyl)acetonitrile Leading to (1R, 2R)- and (1S, 2S)-Bis(pentafluorophenyl)ethane-1, 2-diol"The Journal of Organic Chemistry. (in press).
  • Description: 「研究成果報告書概要(欧文)」より