Elusive 2H-1,2-oxasiletes through reactions of an isolable dialkylsilylene with diazocarbonyl compounds
Elusive 2H-1,2-oxasiletes through reactions of an isolable dialkylsilylene with diazocarbonyl compounds
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通过可分离的二烷基亚甲硅基与重氮羰基化合物的反应获得难以捉摸的 2H-1,2-氧杂硅酸盐
DOI：
10.1039/c5ob01224d
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发表时间：
2015-01-01
影响因子：
3.2
通讯作者：
Kira, Mitsuo
中科院分区：
文献类型：
--
作者：
Dong, Zhaowen;Xiao, Xu-Qiong;Kira, Mitsuo
可分离的二烷基亚硅基1与2-重氮-1，2-二苯基乙酮和2-重氮-2-苯乙酸乙酯反应，高产率地分别得到了难以捉摸的硅杂环化合物2 H-1，2-oxasiletes 2和3。因为这些反应发生在约100 ℃的低温下。在-30 ℃时，亚甲硅烷基与重氮羰基化合物的羰基氧的初始络合被建议引发二氮消除，然后环化。相反，通过1与反应性较低的2-重氮基-3-氧代-3-苯基丙酸乙酯7和三甲基甲硅烷基重氮甲烷9反应，以良好的产率获得六元环状重氮化合物8和1-硅杂-2，3-二氮杂双环[3.3.0]辛-3-烯10。通过X射线晶体学测定了2、3、8和10的分子结构。
The reactions of isolable dialkysilylene 1 with 2-diazo-1,2-diphenylethanone and ethyl 2-diazo-2-phenylacetate gave elusive silacycles, 2H-1,2-oxasiletes 2 and 3, respectively, in high yields. Because these reactions occur at low temperatures of ca. -30 degrees C, initial complexation of the silylene to the carbonyl oxygen of the diazocarbonyl compounds is suggested to trigger dinitrogen elimination followed by cyclization. In contrast, a six-membered cyclic diazo compound 8 and 1-sila-2,3-diazabicyclo[3.3.0]oct-3-ene 10 were obtained in good yields by the reaction of 1 with less reactive ethyl 2-diazo-3-oxo-3-phenylpropanoate 7 and trimethylsilyldiazomethane 9. Molecular structures of 2, 3, 8 and 10 were determined by X-ray crystallography.