| Project/Area Number |
07555276
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| Research Category |
Grant-in-Aid for Scientific Research (A)
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| Allocation Type | Single-year Grants |
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| Section | 展開研究 |
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| Research Field |
有機工業化学
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| Research Institution | University of Tsukuba |
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Principal Investigator |
HOSOMI Akira University of Tsukuba, Chemistry, Professor, 化学系, 教授 (00004440)
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| Co-Investigator(Kenkyū-buntansha) |
TOMINAGA Yoshinori Nagasaki University, Chemistry, Assistant, 薬学部, 助手 (70100881)
HAYASHI Nobuyuki Hitachi Chemical Industries, Co.Ltd., Research Manager, ・筑波開発研究所, 所長
ITO Hajime University of Tsukuba, Chemistry, Assistant, 化学系, 助手 (90282300)
MIURA Katsukiyo University of Tsukuba, Chemistry, Lecturer, 化学系, 講師 (20251035)
HOJO Makoto University of Tsukuba, Chemistry, Lecturer, 化学系, 講師 (50229150)
DHOGANE Iwao Sumitomo Chemical Industries, Co.Ltd., Research Manager
銅金 巌 住友化学工業(株), 有機合成研究所, 所長
顕谷 忠俊 住友化学工業(株), 有機合成研究所, 主席研究員
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| Project Period (FY) |
1995 – 1997
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| Project Status |
Completed (Fiscal Year 1997)
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| Budget Amount *help |
¥9,700,000 (Direct Cost: ¥9,700,000)
Fiscal Year 1997: ¥1,300,000 (Direct Cost: ¥1,300,000)
Fiscal Year 1996: ¥1,600,000 (Direct Cost: ¥1,600,000)
Fiscal Year 1995: ¥6,800,000 (Direct Cost: ¥6,800,000)
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| Keywords | 1,3-Dipolar / Vinylsilane / Carbonyl ylides / Reductive metalation / Manganese Ate Complexe / Samarium-mediated reactions / [3+2] Cycloaddition / Manganese Enolate / 1,3-双極子 / ジヒドロフラン / テトラヒドロフラン / ヨードメチル(シリル)エーテル / 環価付加反応 / サマリウム / 対称オキシラン / 非安定化カルボニルイリド / テトラヒドロフラン合成 / ジヒドロフラン合成 / 合成等価体 / 有機合成 / 1,3-双極子試薬 / 立体特異的合成 |
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| Research Abstract |
The following results are obtained in this research project.
1.Manganese Ate Complexes as a New Reducing Agent : Perfectly Regiocontrolled Generation and Reactions of the Mn-Enolates with Electrophiles
Manganese (II) ate complexes cleanly react with carbonyl compounds bearing a leaving group at the alpha position to generate the enolates of the original ketones, esters, and amides, irrespective of their structure, where the manganate serves as a reductant not an alkylation agent. In this reductive generation of the enolates based on the novel reactivity of the manganese ate complexes, a kind of oxidative addition of a substrate to the ate complex and the reductive elimination of the ligands on manganese are possibly involved as the key processes, while the process equivalent to "metal-halogen exchange" does not seem to be significant. The generality of this reaction was demonstrated in the generation of the enolates of not only aromatic ketones and aliphatic ketones but also an aliphatic
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ester and amide. As for the synthetic value, this reaction was successfully applied to the perfectly regiospecific generation and reactions of a pair of the regioisomeric enolates corresponding to the unsymmetrical and non-branched aliphatic ketones.
2.Unprecedented Samarium-Mediated Reactions : Generation of Non-Stabilized Carbonyl Ylids
Samarium reveals a strong reducing ability and by virtue of this character together with its oxophilicity, is widely applied to organic synthesis in the formation of carbon-carbon bonds and transformation of a variety of functionalities with high selectivities. In the course of our study on the generation and reactions of reactive species, we report herein the generation of novel active species, non-stabilized carbonyl ylids from iodomethyl silyl ethers mediated by samarium, otherwise inaccessible, and their [3+2] cycloadditions to a variety of unsaturated compounds such as aldehydes, alkenes, allenes, and alkynes.
3.Silicon-Directed Cyclization of Vinylsilanes Bearing Hydroxy Group Catalyzed by an Acid
The acid-catalyzed cyclization of vinylsilanes bearing a hydroxy group took place cleanly to give tetrahydrofurans and tetrahydropyrans, and the addition of hydroxy group to vinylsilane proceeded in a syn stereoselective fashion. Less
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