| Project/Area Number |
19350048
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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 | 一般 |
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| Research Field |
Synthetic chemistry
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| Research Institution | Gifu University |
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Principal Investigator |
MURAI Toshiaki Gifu University, 工学部, 教授 (70166239)
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| Co-Investigator(Kenkyū-buntansha) |
SHIBAHARA Fumitoshi 岐阜大学, 工学部, 助教 (60362175)
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| Project Period (FY) |
2007 – 2010
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| Project Status |
Completed (Fiscal Year 2010)
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| Budget Amount *help |
¥18,330,000 (Direct Cost: ¥14,100,000、Indirect Cost: ¥4,230,000)
Fiscal Year 2009: ¥4,810,000 (Direct Cost: ¥3,700,000、Indirect Cost: ¥1,110,000)
Fiscal Year 2008: ¥4,810,000 (Direct Cost: ¥3,700,000、Indirect Cost: ¥1,110,000)
Fiscal Year 2007: ¥8,710,000 (Direct Cost: ¥6,700,000、Indirect Cost: ¥2,010,000)
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| Keywords | キラル分子ツール / セレノリン酸塩化物 / セレノリン酸エステル / セレノリン酸塩 / フッ素化加水分解 / セレリン酸クロリド / 絶対配置 / 光学分割 / BISEPCl / 絶対配置決定 / ジアステレオマー混合物 / 31P NMR / 77Se NMR / BISEPCI |
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| Research Abstract |
Methods for the discrimination of secondary optically active alcohols with aliphatic substituents and for the synthesis of optically active cyclic amines have been developed. As a key starting material, phosphoroselenoyl chloride with optically active 1,1'-2-binaphthyl groups are used. The reaction of the chlorides with alcohols proceeded smoothly to give the corresponding esters. The general tendency of the 1^H, <13>^C, <31>^P, and <77>^Se NMR spectra of the esters was disclosed, and on the basis of these values, the method for the determination of the absolute configuration of secondary alcohols was established. The reaction of esters with amines proceeds with the inversion of the configuration at the carbon atom attached to the oxygen atom. With this properties, the ester derived from a diol was reacted with benzylamine to leads to 2-alkylpiperidine in good yield. The chloride was converted to phosphoroselenoic acids and their salts. The acids were tested as organocatalysts. During these studies, the high affinity of the fluorine atom toward the phosphorus atom was revealed. With this property, the fluoridative hydrolysis of phosphoric acid esters was achieved to give phosphorofluoridate monoesters with high efficiency.
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