Nucleophilic addition to silyl-protected five-membered ring oxocarbenium ions governed by stereoelectronic effects.
Nucleophilic addition to silyl-protected five-membered ring oxocarbenium ions governed by stereoelectronic effects.
复制标题
受立体电子效应控制的甲硅烷基保护的五元环氧碳鎓离子的亲核加成。
DOI：
10.1021/jo400945j
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发表时间：
2013
期刊：
影响因子：
--
通讯作者：
Woerpel,KA
中科院分区：
文献类型：
--
作者：
Tran,ViTuong;Woerpel,KA
研究了一系列含有二硅氧烷环的融合双环缩醛，以评价硅基保护的2-脱氧核糖体系的选择性来源。出乎意料的是，二硅氧烷环使得阳离子的双轴构象被C-3上的电负性原子所稳定。该低能构象随后经过立体电子控制的亲核加成得到具有高非对映选择性的取代四氢呋喃。
A series of fused-bicyclic acetals containing a disiloxane ring was investigated to evaluate the source of selectivity in silyl-protected 2-deoxyribose systems. The disiloxane ring unexpectedly enables the diaxial conformer of the cation to be stabilized by an electronegative atom at C-3. This low energy conformer subsequently undergoes stereoelectronically controlled nucleophilic addition to give substituted tetrahydrofurans with high diastereoselectivity.