Divergent Synthesis of Polysubstituted Cyclopropanes and β-Silyoxy Imidates via Switchable Additions of N-tert-Butanesulfinylimidates to Acylsilanes
Divergent Synthesis of Polysubstituted Cyclopropanes and β-Silyoxy Imidates via Switchable Additions of N-tert-Butanesulfinylimidates to Acylsilanes
复制标题
通过将 N-叔丁烷亚磺酰亚胺酯可切换地添加到酰基硅烷中，不同合成多取代环丙烷和 β-甲硅烷氧基亚胺酯
DOI：
10.1039/c9cc00963a
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发表时间：
2019
影响因子：
4.9
通讯作者：
Lu Chong-Dao
中科院分区：
文献类型：
--
作者：
Tang Fan;Ma Peng-Ju;Yao Yun;Xu Yan-Jun;Lu Chong-Dao
N-叔丁基亚磺酰亚胺与酰基硅烷反应生成的产物可以通过选择合适的碱和溶剂进行调节。在NaHMDS/四氢呋喃存在下，烯醇化的N-叔丁基亚磺酰亚胺与酰基硅烷加成，随后的[1，2]-Brook重排生成β-硅氧基阴离子中间体，该中间体经过分子内环合反应得到多取代环丙烷。在tBuOK/甲苯存在下，反应生成β-硅氧基酰亚胺，作为β-硅氧基阴离子中间体的质子化产物。这两个反应都是高度非对映选择性的。
Products derived from the reaction between N-tert-butanesulfinyl imidates and acylsilanes can be tuned by choosing appropriate bases and solvents. Here we show that in the presence of NaHMDS/THF, addition of enolized N-tert-butanesulfinyl imidates to acylsilanes and subsequent [1,2]-Brook rearrangement generate β-silyloxy anion intermediates that undergo intramolecular cyclization to afford polysubstituted cyclopropanes. In the presence of tBuOK/toluene, the reaction generates β-silyloxy imidates as the protonation products of the β-silyloxy anion intermediates. Both reactions are highly diastereoselective.