Diverse reactivity of an isolable dialkylsilylene toward imines
Diverse reactivity of an isolable dialkylsilylene toward imines
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可分离的二烷基亚甲硅基对亚胺的多种反应性
DOI：
10.1039/c2dt32126b
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发表时间：
2013-01-01
影响因子：
4
通讯作者：
Kira, Mitsuo
中科院分区：
文献类型：
--
作者：
Chen, Weifeng;Wang, Liliang;Kira, Mitsuo
可分离的二烷基亚硅基10与各种醛亚胺的反应在低温下顺利进行，根据亚胺上的取代基得到不同的产物。10与4-XC 6 H4 CH =NPh [X = H（11 a），MeO（11 b）和Cl（11 c）]的反应以高产率得到相应的硅氮杂环丙烷12 a-12 c，它们是非常热稳定的，并且在空气和湿气中长时间保持完整。相反，10与4-F3 CC 6 H4 CH =NPh（11 d）和在亚胺碳上具有强吸电子芳基取代基的3，5-（F3 C）（2）C6 H3CH =NPh（11 e）的反应伴随着1，2-三甲基甲硅烷基迁移，相当出乎意料地得到并入双环[3.2.0]庚烷环中的硅氮杂环丁烷13 d-13 e。10与N-苄基苯甲醛亚胺11 f的反应以中等产率得到相应的（二苄基氨基）硅烷14 f。通过X射线晶体学测定了12 a-12 c、13 d-13 e和14 f的分子结构。所有这些反应都是通过最初形成相应的亚胺硅化物而发生的，而随后的反应导致最终产物是由叶立德的电子结构控制的，取决于取代基。N-苯基二苯甲亚胺Ilg不与10反应。
The reactions of isolable dialkylsilylene 10 with various aldimines proceed smoothly at low temperatures to give diverse products depending on the substituents on the imine. The reactions of 10 with 4-XC6H4CH=NPh [X = H (11a), MeO (11b), and Cl (11c)] give the corresponding silaaziridines 12a-12c in high yields, which are thermally very stable and remain intact in the air and moisture for a long time. In contrast, the reactions of 10 with 4-F3CC6H4CH=NPh (11d) and 3,5-(F3C)(2)C6H3CH=NPh (11e) having strong electron-withdrawing aryl substituents on imine carbon are accompanied by 1,2-trimethylsilyl migration rather unexpectedly to give silaazetidines 13d-13e incorporated into a bicyclo[3.2.0]heptane ring. The reaction of 10 with N-benzylbenzaldimine 11f affords the corresponding (dibenzylamino)silane 14f in a moderate yield. Molecular structures of 12a-12c, 13d-13e and 14f were determined by X-ray crystallography. All these reactions are proposed to occur via the initial formation of the corresponding imine silaylides, while the subsequent reactions leading to the final products are controlled by the electronic structure of the ylide depending on the substituents. N-Phenylbenzophenimine 11g does not react with 10.