Development of New Functionalized Nitrile Oxides and Their Synthetic Application
| Project/Area Number |
61470095
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| Research Category |
Grant-in-Aid for General Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Research Field |
Synthetic chemistry
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| Research Institution | Kyushu University |
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Principal Investigator |
TSUGE Otohiko Institute of Advanced Material Study, Kyushu University, 機能物質科学研究所, 教授 (00038572)
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| Co-Investigator(Kenkyū-buntansha) |
KANEMASA Shuji Institute of Advanced Material Study, Kyushu University, 機能物質科学研究所, 助教授 (20038590)
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| Project Period (FY) |
1986 – 1987
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| Project Status |
Completed (Fiscal Year 1987)
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| Budget Amount *help |
¥5,000,000 (Direct Cost: ¥5,000,000)
Fiscal Year 1987: ¥1,500,000 (Direct Cost: ¥1,500,000)
Fiscal Year 1986: ¥3,500,000 (Direct Cost: ¥3,500,000)
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| Keywords | Phosphorus-functionalized acetonitrile oxide / Sulfur-functionalized acetonitrile oxide / 1,3-Depolar Cycloaddition / <beta>-Hydroxy ketones / <alpha>, <beta>-Unsaturated ketones 2-Phosphorus- functionalized Furns / 2-リン官能化フラン / 5-リン官能化3(2H)-フラノン / 官能化ニトリルオキシド / ホスホノアセトニトリルオキシド / フェニルチオアセトニトリルオキシド / 官能化イソオキサゾリン / 官能化イソオキサゾール / アルケニルフラノン / ガイパルバリン |
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| Research Abstract |
The methods for the generation of new functionalized nitrile oxides, (diethoxyphosphoryl)- 1 and (phenylthio)acetonitrile oxide 2 were developed.
Cycloaddition of the nitrile oxides 1 and 2 to mono-substituted olefins proceeded regio selectively to give 5-substituted 3-phosphorus- and 3-sulfur-fuctionalized 2-isoxazolines, respectively. The phosphorus- and sulfur-stabilized carbanions generated by selective deprotonation of the cycloadducts could be utilized for the alkylation, olefination, and Michael addition. Raney nickel hydrogenolysis of the 2-isoxazolines gave functionalized <beta>-hydroxy ketones and <alpha>,<beta>- unsaturated ketones. Hese methods were applied for the synthesis of (<plus-minus>)-Gingerol, (<plus-minus>)- Yashabushiketol and (<plus-minus>)-Dihydroyashabushiketol.
The nitrile oxide 1 underwent cycloaddition to allyl tetrahydropyranyl ethers in a regioselective manner to give the 2-isoxazolines. Hydrogenolysis of the cycloadducts, followed by dehydrative cyclization afforded 2-phosphorus-functionalized furans bearing substituent(s) orginated from allyl alcohols at 3-, 4- and/or 5-positions. Synthetic methods for 2-alkenylfurans was developed, and this procedure was applied to the synthesis of a natural product, Furanosesquiterpene.
Cycloaddition of nitrile oxide 1 to acetylene alcohols, followed by alkylation of the isoxazoles, reductive cleavagem and acid-catalized cyclization gavs 5-phosphorus-functionalized 3(2H)-furanones. Subsequent Horner-Emmons olefination gave 5-(1-alkenyl)-3(2H)-furanones. This method was applied to short synthesis of Geiparvarin.
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Report
(2 results)
Research Products
(13 results)
