Use of an aminosilyllithium for the diastereoselective synthesis of diphenyl oxasilacyclopentane acetals and polyols.
Use of an aminosilyllithium for the diastereoselective synthesis of diphenyl oxasilacyclopentane acetals and polyols.
复制标题
氨基甲硅烷基锂用于二苯基氧杂硅环戊烷缩醛和多元醇的非对映选择性合成的用途。
DOI：
10.1021/ol035577a
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发表时间：
2003
期刊：
影响因子：
--
通讯作者：
Woerpel,KA
中科院分区：
文献类型：
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作者：
Tenenbaum,JasonM;Woerpel,KA
稳定的原位生成的硅基锂的共轭加成反应得到具有高非对映选择性的β-羟基硅酯。将β-羟基甲硅烷基酯转化为β-氟甲硅烷基酯在温和条件下以高产率提供氧杂硅杂环戊烷缩醛的前体。氢化物还原和随后的分子内甲硅烷基化以优异的产率得到缩醛。最后，高选择性的亲核取代得到氧杂硅杂环戊烷，其经历温和的氧化以高选择性得到1，3-反式二醇。
The conjugate addition reaction of a stable, in situ generated silyllithium gives a β-hydroxysilyl ester with high diastereoselectivity. Conversion of the β-hydroxysilyl ester to a β-fluorosilyl ester affords the precursor to the oxasilacyclopentane acetal in high yields under mild conditions. A hydride reduction and subsequent intramolecular silylation lead to the acetal in excellent yields. Finally, highly selective nucleophilic substitution affords oxasilacyclopentanes, which undergo a mild oxidation to afford 1,3-trans diols with high selectivity.