ENANTIOSELECTIVE CONSTRUCTION OF DIALKYLCARBINOLS - SYNTHESIS OF (-)-5-HEXADECANOLIDE
ENANTIOSELECTIVE CONSTRUCTION OF DIALKYLCARBINOLS - SYNTHESIS OF (-)-5-HEXADECANOLIDE
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DOI：
10.1021/ja00258a039
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发表时间：
1987-11-25
影响因子：
15
通讯作者：
GAUL, MD
中科院分区：
文献类型：
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作者：
TABER, DF;DEKER, PB;GAUL, MD
醇2被设计成封闭衍生的β-环己基中羰基的一个面。酮酯3.然后，氢化物还原可以通过其中羰基是顺式的过渡态（ZnCl 2/Zn（BH 4）2，4：5 = 92：8）或通过其中羰基是反式的替代过渡态（Dibal.sbd.BHT，4：5 = 4：96）进行。从LiAlH 4还原5的1，3-二醇的伯甲苯磺酸酯的烷基偶联然后打开了二烷基甲醇的一般对映选择性路线。
Alcohol 2 is designed to block one face of the carbonyls in the derived .beta.-keto ester 3. Hydride reduction can then proceed either via the transition state in which the carbonyls are syn (ZnCl2/Zn(BH4)2, 4:5 = 92:8) or via the alternative transition state in which the carbonyls are anti (Dibal.sbd.BHT, 4:5 = 4:96). Alkyl coupling of the primary tosylate of the 1,3-diol from LiAlH4 reduction of 5 then opens a general enantioselective route to dialkylcarbinols.