A Short Sequence for the Iterative Synthesis of Fused Polyethers

A Short Sequence for the Iterative Synthesis of Fused Polyethers
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稠合聚醚迭代合成的短流程

DOI:
10.1002/hlca.201900161
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发表时间:
2019
影响因子:
1.8
通讯作者:
Elustondo F
Elustondo F
中科院分区:
化学4区
文献类型:
--
作者:
Elustondo F

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提出了一种合成稠合聚醚阵列的简单有效的四步合成方法。环醚是通过连续的炔基醚形成、碳铜化、闭环歧化和加氢硼化加酸性处理来安装的。关键的是,随后通过闭环歧化形成环所需的烯烃存在于底物中,但以乙烯基硅烷的形式被掩盖,这防止了侧链的竞争性歧化。从未反应的乙烯基硅烷中生成反应性烯烃是通过氢化硼化反应和随后的酸中介彼得森消除中间体羟基硅烷来完成的。
A simple and efficient four‐step sequence for the synthesis of fused polyether arrays has been developed. Cyclic ethers are installed by sequential alkynyl ether formation, carbocupration, ring‐closing metathesis and hydroboration with acidic workup. Crucially, the alkene required for the subsequent ring formation by ring‐closing metathesis is present in the substrate but is masked in the form of a vinylic silane, which prevents competitive metathesis of the side chain. Generation of the reactive alkene from the unreactive vinylic silane is accomplished by hydroboration and subsequent acid‐mediatedPetersonelimination of the intermediate hydroxysilane.
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