Simple Designs for the Construction of Complex Trans-Fused Polyether Toxin Frameworks. A Convergent Strategy Based on Hydroxy Ketone Cyclization of C-Linked Oxacycles.
Simple Designs for the Construction of Complex Trans-Fused Polyether Toxin Frameworks. A Convergent Strategy Based on Hydroxy Ketone Cyclization of C-Linked Oxacycles.
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构建复杂转融合聚醚毒素框架的简单设计。
DOI：
10.1002/chin.199636026
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发表时间：
1996
期刊：
影响因子：
--
通讯作者：
Julio D. Martín
中科院分区：
文献类型：
--
作者：
E. Álvarez;R. Pérez;M. Rico;R. Rodríguez;Julio D. Martín
提出了一种单一的、统一的聚醚立体控制合成策略。结果表明，羟基酮与硅烷-路易斯酸（SI-LA）在c -氧环上生成醚的外映和分子内还原偶联反应受其构象偏好的影响。所得结果表明，半晶羟基和1,3-二轴C-O键之间的氢键的影响是规则的和可预测的，在热力学条件下，可以自信地进行聚醚的聚合合成，以驱动环闭合到氧环
A single, unified convergent strategy for the stereocontrolled synthesis of trans-fused polyethers was developed. It was demonstrated that the epimerization and reductive intramolecular coupling of hydroxy ketones in reactions with silane-Lewis acids (SI-LA) to generate ethers in C-linked oxacycles is affected by its conformational preference in a predictable manner. The obtained results make evident that the influence of hydrogen bonding between a hemiketal hydroxyl and a 1,3-diaxial C-O bond is regular and predictable and that convergent synthesis of trans-fused polyethers may confidently be conducted on driving ring closure to oxane rings under thermodynamic conditions