摘要
合成了(S)-3-羟基哌啶苯硫醚化合物6作为3-羟基哌啶氮α-碳负离子手性合成子(B)的合成等效体.化合物6经羟基去质子现场保护、萘锂(LN)还原锂化形成手性哌啶醇双负离子中间体B.双负离子B可被质子淬灭得到还原产物2a;而与羰基化合物反应则得到α-羟烷化产物12～17和少量还原产物2a.该反应具有很高的环上2,3-位非对映立体选择性;与非对称的羰基化合物反应产生新手性中心的立体选择性从50:50到77:23.
The （S）-sulfide 6 was synthesized as a synthetic equivalent of novel 3-piperidinol N-α-carbanion B, via deprotonation and lithium naphthanelide （LN）-mediated reductive lithiation. The reaction of the 3-piperidinol N-α-carbanion intermediate B with carbonyl compounds gave, besides some reduced product 2a, the desired α-hydroxyalkylation products 12-17 with excellent 2,3-diastereoselectivity. The reductive α-hydroxyalkylation with unsymmetric carbonyl compounds led to only 50：50 to 77：23 diastereoselectivities at the C-1＇ carbinol center.
出处
《中国科学（B辑）》
CSCD
北大核心
2009年第10期1175-1183,共9页
Science in China(Series B)
基金
国家自然科学基金(批准号:20832005)资助
关键词
苯硫醚
氮α位碳负离子
还原锂化
α-羟烷化
非对映立体选择性
sulfide, N-α-carbanion, lithium-naphthanelide, reductive lithiation, carbonyl compounds, α-hydroxyalkylation, diastereoselectivity
