| Project/Area Number |
10672015
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Chemical pharmacy
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| Research Institution | RIKEN (The Institute of Physical and Chemical Research) |
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Principal Investigator |
SHIMIZU Takeshi RIKEN, SYNTHETIC ORGANIC CHEMISTRY LABORATORY, SENIOR RESEARCH SCIENTIST, 有機合成化学研究室, 先任研究員 (80087569)
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| Co-Investigator(Kenkyū-buntansha) |
SAKAMOTO Yasuharu RIKEN, SYNTHETIC ORGANIC CHEMISTRY LABORATORY, RESEARCH SCIENTIST, 有機合成化学研究室, 研究員 (60280723)
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| Project Period (FY) |
1998 – 1999
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| Project Status |
Completed (Fiscal Year 1999)
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| Budget Amount *help |
¥3,300,000 (Direct Cost: ¥3,300,000)
Fiscal Year 1999: ¥900,000 (Direct Cost: ¥900,000)
Fiscal Year 1998: ¥2,400,000 (Direct Cost: ¥2,400,000)
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| Keywords | rearrangement-ring expansion of cyclic ether / chloromethanesulfonate / monochlate / invertion of secondary alcohol / rearrangement of carbon-carbon bond / azide / carbon-nitrogen bond formation / nitrile / テトラヒドロピラン / 炭素-炭素結合形成反応 / 環状エーテルの転位-環拡大反応 / オキセパン / ビシクロオキソニウムイオン / 二級水酸基の反転反応 / 炭素-窒素結合形成反応 / 炭素-炭素結合の転位反応 |
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| Research Abstract |
One of the important and most widely studied organic reactions is nucleophilic substitution at a saturated carbon. Although sulfonates are the most common leaving groups, we sometimes encounter problems such as low reactivity of the methanesulfonates (mesylates; Ms=CHィイD23ィエD2SOィイD22ィエD2-) and instability of the trifluoromethanesulfonates (triflates; Tf=CFィイD23ィエD2SOィイD22ィエD2-). We have found that chloromethanesulfonates (monochlate; Mc=C1CHィイD22ィエD2SOィイD22ィエD2-) served as an extremely efficient leaving group, which exceeds the corresponding mesylates and triflates. Inversion of a wide range of secondary alcohols using the monochlates with cesium acetate in the presence of 18-crown-6 in benzene under reflux has been performed to give the acetates with complete inversion of the configuration in high yields. We have examined further studies on the monochlate as the new and efficient leaving group and found several efficient reactions using monochlates; i.e., (1) rearrangement of the carbon-carbon bond, (2) conversion of secondary alcohols into azides with inversion of the configuration, and (3) conversion of a β-alkoxy primary alcohol into a nitrile.
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