1999 Fiscal Year Final Research Report Summary
Synthesis of Optically Active Compounds Having Pentafluorophenyl Group - The Structure and Function
| Project/Area Number |
10555321
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 展開研究 |
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| Research Field |
Synthetic chemistry
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| Research Institution | Okayama University |
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Principal Investigator |
UTAKA Masanori Okayama University, Faculty of Engineering, Professor, 工学部, 教授 (30033153)
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| 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)
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| Project Period (FY) |
1998 – 1999
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| Keywords | fluorine / optically active / diol / amino alcohol / lipase |
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| 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.
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