Development of Novel Synthetic Reactions with Organomagnesium Reagents
Development of Novel Synthetic Reactions with Organomagnesium Reagents
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有机镁试剂新型合成反应的进展
DOI：
10.5059/yukigoseikyokaishi.61.331
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发表时间：
2003
影响因子：
0.2
通讯作者：
K. Oshima
中科院分区：
文献类型：
--
作者：
A. Inoue;H. Shinokubo;K. Oshima
β-碘代烯丙基缩醛与EtMgBr在THF中反应得到四氢呋喃衍生物。另一方面，在DME中的反应提供了（3-四氢呋喃基）甲基镁物种，可以被各种亲电试剂捕获。用EtMgBr和碘代烷烃在THF中处理芳基镁物质得到2-芳基四氢呋喃。nBu 3 MgLi在-78 ° C诱导容易的碘-镁交换。iPrnBu 2 MgLi比nBu 3 MgLi更具反应性，并且该试剂在-78 ° C下实现选择性溴-镁交换。该程序用于制备各种多官能化芳基镁物质。使用该方法进行的烯基卤化物的交换保留了双键处的构型。偕-二溴环丙烷与nBu 3 MgLi的反应提供了可以用各种亲电试剂捕获的丁基化环丙基镁物种。二溴甲基硅烷与nBu 3 MgLi在催化量CuCN 2LiCl存在下反应生成α-硅基戊基镁化合物，后者与亲电试剂如酰氯或α，β-不饱和酮反应分别生成α-或γ-硅基酮.用Me 3 MgLi处理二溴二甲硅烷基甲烷产生1-溴-1，1-二甲硅烷基乙烷，其可通过脱溴化氢转化为1，1-二甲硅烷基乙烯。
The reaction of β-iodo allylic acetals with EtMgBr in THF afforded tetrahydrofuran derivatives. On the other hand, the reaction in DME provided (3-tetrahydrofuryl) methylmagnesium species that could be trapped by a variety of electrophiles. Treatment of arylmagnesium species with EtMgBr and iodoalkanes in THF afforded 2-aryltetrahydrofurans.nBu3MgLi induces facile iodine-magnesium exchange at -78°C. iPrnBu2MgLi is more reactive than nBu3MgLi, and this reagent accomplishes selective bromine-magnesium exchange at -78°C. This procedure was utilized for the preparation of various polyfunctionalized arylmagnesium species. The exchange of alkenyl halides using this method proceeds with retention of configuration at the double bond. The reaction of gem-dibromocyclopropanes with nBu3MgLi affords butylated cyclopropylmagnesium species that can be trapped with various electrophiles. The reaction of dibromomethylsilanes with nBu3MgLi in the presence of a catalytic amount of CuCN 2 LiC1 gives α-silylpentylmagnesium compounds that react with electrophiles such as acyl chlorides or α, β-unsaturated ketones to afford α- or γ-silyl ketones respectively. Treatment of dibromodisilylmethanes with Me3MgLi yields 1-bromo-1, 1-disilylethanes that can be converted into 1, 1-disilylethenes by dehydrobromination.