Synthesis of α-hydroxy-β,β-difluoro-γ-ketoesters via [3,3]sigmatropic rearrangements
Synthesis of α-hydroxy-β,β-difluoro-γ-ketoesters via [3,3]sigmatropic rearrangements
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通过[3,3]σ重排合成α-羟基-β,β-二氟-γ-酮酯
DOI：
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发表时间：
2000
期刊：
影响因子：
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通讯作者：
M. Prime
中科院分区：
文献类型：
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作者：
M. Broadhurst;Samantha J. Brown;J. Percy;M. Prime
以三氟乙醇为原料合成了易得的γ，γ-二氟烯丙醇，并进行了高效的酯化反应。暴露在强碱(LDA)中提供了酯烯醇酸盐，其中的螯合作用既控制了构型又稳定了防止碎裂，这些烯醇酸酯以硅基酮缩醛的形式被捕获。为了得到碱敏感的酸产品，发生了重排。在温和的条件下酯化得到了可提纯的甲酯，其中掩蔽酮已被释放。在α-位带有苄氧基或烯丙氧基的产物可能会被解除保护，释放出醇。
Readily available γ,γ-difluorinated allylic alcohols obtained from trifluoroethanol were esterified efficiently. Exposure to strong base (LDA) afforded the ester enolates, in which chelation both controlled configuration and stabilised against fragmentation, which were trapped as their silyl ketene acetals. Rearrangement occurred to afford base-sensitive acid products. Esterification under mild conditions afforded the purifiable methyl esters in which the masked ketone had been released. Educts with either a benzyloxy or an allyloxy group at the α-position could be deprotected releasing the alcohols.
具有 10 A 间距的定向芳基和醇附属物的 C(3)-对称氢吡喃环低聚内酯的合成和研究。
DOI：
10.1021/jo991681n
发表时间：
2000
期刊：
The Journal of organic chemistry
影响因子：
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作者：
Burke,SD;Zhao,Q
通讯作者：
Zhao,Q