1996 Fiscal Year Final Research Report Summary
1,1-, 1,2-, and 1,4-Eliminations from the Corresponding Dihalogenated Compounds Using Bu_3SnSiMe_3-F^-
| Project/Area Number |
06453185
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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 |
Chemical pharmacy
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| Research Institution | HOKKAIDO UNIVERSITY |
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Principal Investigator |
MORI Miwako Hokkaido Univ., Fac.of Pharm., Professor, 薬学部, 教授 (80001981)
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| Co-Investigator(Kenkyū-buntansha) |
SATO Yoshihiro Hokkaido Univ., Fac.of Pharm., Instructor, 薬学部, 助手 (90226019)
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| Project Period (FY) |
1994 – 1996
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| Keywords | Me_3SiSnBu_3 / C-3 elongation / Methyl bistributylstannyl propionate / Methyl propiolate / gamma-elimination / 8-membered ring / 3-membered ring |
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| Research Abstract |
We have already reported the generation of stannyl anion from Me_3SiSnBu_3 in the presence of CsF in DMF and the utilization of this stannyl anion for the novel cyclization via halogen-metal exchange reaction. It was expected that the active intermediates would be produced from the corresponding dihalo-compounds by 1,1-, 1,2-, or 1,4-elimination. At first, when alpha, alpha'-dibromo-o-xylene was treated with Me_3SiSnBu_3 and CsF in the presence of methyl acrylate in DMF,2-carbomethoxy tetrahydronaphthalene was obtained in 87% yield. In a similar manner, the various tetrahydronaphthalene derivatives were obtained in good yields. On the other hand, benzyne was produced from 1,2-dibromobenzene. This reaction was further developed for the generation of alkylidene carbene from 1,1-dibromoalkene, and we could obtained alkenes or cyclopentenone derivatives from the crresponding 1,1-dibromoalkene in good to moderate yields.
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