Generation and α-hydroxyalkylation of a novel 3-piperidinol N-α-carbanion intermediate  

作　　者：ZHENG Xiao CHEN Guo RUAN YuanPing HUANG PeiQiang 

机构地区：[1]Department of Chemistry and Key Laboratory for Chemical Biology of Fujian Province,College of Chemistry and Chemical Engineering,Xiamen University,Xiamen 361005,China

出　　处：《Science China Chemistry》2009年第10期1631-1638,共8页中国科学（化学英文版）

基　　金：Supported by the National Natural Science Foundation of China (Grant No. 20832005)

摘　　要：The (S)-sulfide 6 has been 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.The (S)-sulfide 6 has been 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.

关 键 词：sulfide N-α-carbanion lithium-naphthanelide reductive LITHIATION CARBONYL compounds α-hydroxyalkylation DIASTEREOSELECTIVITY 

分 类 号：O621.2[理学—有机化学]