1,1-, 1,2-, and 1,4-Eliminations from the Corresponding Dihalogenated Compounds Using Bu_3SnSiMe_3-F^-

使用 Bu_3SnSiMe_3-F^- 从相应的二卤代化合物中消除 1,1-、1,2- 和 1,4-

• 批准号: 06453185
• 负责人: MORI Miwako
• 金额: $ 4.74万
• 依托单位: HOKKAIDO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1994
• 资助国家: 日本
• 起止时间: 1994 至 1996
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-06453185/
• 关键词: Me_3SiSnBu_3; C-3 elongation; Methyl bistributylstannyl propionate; Methyl propiolate; gamma-elimination; 8-membered ring; 3-membered ring; ベンザイン; 1,2-ジブロモベンゼン; TASF; CsF; フラン; Diels-Alder反応; オルトキノジメタン; 環化反応; [2+4]cycloaddition

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.

我们已经报道了在DMF中CsF存在下Me_3SiSnBu_3生成锡基阴离子，并利用该锡基阴离子通过卤素-金属交换反应进行新的环化反应。预期相应的二卤化合物可通过1,1-、1,2-或1,4消去制得活性中间体。首先，在DMF中丙烯酸甲酯存在的情况下，用Me_3SiSnBu_3和CsF处理α， α′-二溴-邻二甲苯，得到2-碳甲氧基四氢萘，收率为87%。用同样的方法，得到了各种四氢萘衍生物，收率很高。另一方面，苯是由1,2-二溴苯生成的。将该反应进一步发展为由1,1-二溴烯烃生成烷基烯，并可得到相应的1,1-二溴烯烃的烯烃或环戊酮衍生物，收率较高至中等。

项目成果

Naohiro Isono and Miwako Mori: "Highly Stereocontrolled Cyclopropanation by the 1,3-Elimination of a Bis (tributylstannyl) propanol Derivative" J.Org.Chem.61. 7867-7872 (1996)

Naohiro Isono 和 Miwako Mori：“通过双（三丁基锡基）丙醇衍生物的 1,3-消除实现高度立体控制的环丙烷化”J.Org.Chem.61。

Naohiro Isono and Miwako Mori: "A Novel Carbon-Carbon Bond Forming Reaction Using Bis (tributylstannyl) propanol" Main Group Metal Chemistry. 19. 277-281 (1996)

Naohiro Isono 和 Miwako Mori：“使用双（三丁基锡基）丙醇的新型碳-碳键形成反应”主族金属化学。

Naohiro Isono: "Highly Stereocontrolled Cyclopropanation by the 1, 3-Elimination Bis (tributylstannyl) propanol Derivative" J. Org. Chem.61. 7867-7872 (1996)

Naohiro Isono：“通过 1, 3-消除双（三丁基锡基）丙醇衍生物实现高度立体控制的环丙烷化”J. Org。

Takahiro Honda: "Synthesis of Azazirconacyclopropanes and Azazirconacyclopentenes from η^2-Iminosilaacyl Complexes" Organometallics. 14. 1548-1550 (1995)

Takahiro Honda：“从 η^2-Iminosilaacyl Complexes 合成氮杂氮环丙烷和氮杂氮环戊烯”有机金属学 14。1548-1550 (1995)

Hiroki Yoshizaki: "Palladium Mediated Asymmetric Synthesis of cis-3,6-Disubstituted Cyclohexenes.A Short Total Synthesis of Optically Active(+)-γ-Lycorane" J.Org.Chem.60. 2016-2021 (1995)

Hiroki Yoshizaki：“钯介导的顺式 3,6-二取代环己烯的不对称合成。光学活性 (+)-γ-Lycorane 的简短全合成”J.Org.Chem.60 (1995)。