New synthesis of .alpha.,.beta.-unsaturated aldehydes using 1,3-bis(methylthio)allyllithium
New synthesis of .alpha.,.beta.-unsaturated aldehydes using 1,3-bis(methylthio)allyllithium
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使用1,3-双(甲硫基)烯丙基锂新合成α,β-不饱和醛
DOI：
10.1021/ja00736a027
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发表时间：
1971
影响因子：
15
通讯作者：
R. Noyori
中科院分区：
文献类型：
--
作者：
E. Corey;B. W. Erickson;R. Noyori
1，3-双（甲硫基）-2-甲氧基丙烷（5）（容易从表氯醇分两步获得）与二异丙基氨基锂在四氢呋喃中反应产生1，3-双（甲硫基）-烯丙基阴离子的锂衍生物（1）。由此产生的试剂1已被证明有效地用作未知的β-甲酰乙烯基阴离子的等价物，其通过以烷基卤化物、羰基化合物或1，2-环氧化物为起始物合成许多β，β-不饱和醛来实现。在最后两种底物的情况下，产生三官能γ-或β-羟基，β-不饱和醛单元。这是在前列腺素F2 a的全合成中已经开发的新方法的独特且有用的特征。研究结果表明，试剂1的使用为共轭醛的合成提供了一条新的途径，在许多合成问题上都有一定的优势。
Reaction of l, 3-bis (methylthio)-2-methoxypropane (5)(easily available in two steps from epichlorohydrin) with lithium diisopropylamide in tetrahydrofuran produces the lithio derivative of the 1, 3-bis (methylthio)-allyl anion (1). The reagent 1 so generated has been shown to serve effectively as the equivalent of the unknown/3-formylvinyl anion by thesynthesis of a number of,/3-unsaturated aldehydes starting with alkyl halides, carbonyl compounds, or 1, 2-epoxides. In the case of the last two substrates a trifunctional y-or-hydroxy,/3-unsaturated aldehyde unit results. This is a unique and useful feature of the new method which has been exploited in a total synthesis of prostaglandin F2a. It is concluded from these studies that the use of the reagent 1 represents a signifi-cant new approach to the synthesis of conjugated aldehydes which should be advantageous in a wide range of syn-thetic problems.