Diaryl Ether and Diaryl Thioether Syntheses on Solid Supports via Copper (I)-Mediated Coupling
Diaryl Ether and Diaryl Thioether Syntheses on Solid Supports via Copper (I)-Mediated Coupling
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DOI：
10.1021/cc800032q
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发表时间：
2009-01-01
影响因子：
--
通讯作者：
Braese, Stefan
中科院分区：
文献类型：
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作者：
Jung, Nicole;Braese, Stefan
描述了一种在固相载体上合成二芳基醚和硫醚的有效方法。从固定化苯酚或芳基卤化物开始，在 CuCl 和 Cs2CO3 作为碱存在的情况下，与溶液中的芳基碘化物/芳基溴化物或酚类/苯硫酚底物的偶联成功。二芳基醚溶液相合成中已知的偶联条件已被有效修改并适应于固相合成。优化的条件使得空间位阻和/或电子失活的芳基部分能够偶联。偶联后，新开发的基于肉桂酸的多样性生成连接体允许二芳基醚通过皂化/酯交换或通过臭氧分解从树脂上裂解下来。后者提供了通过简单改变裂解条件来生成几种额外化合物的可能性。目标物质通常以良好至优异的产率和高纯度分离。
An efficient method to synthesize diaryl ethers and thioethers on solid supports is described. Starting from immobilized phenols or arylhalides, coupling with an access of aryliodides/arylbromides or phenolic/thiophenolic substrates in solution was successful in the presence of CuCl and Cs2CO3 as base. Coupling conditions known from solution-phase syntheses of diaryl ethers have been effectively modified and adapted to solid-phase synthesis. Optimized conditions enabled the coupling of sterically hindered and/or electronically deactivated aryl moieties. After coupling, a newly developed diversity-generating linker based on cinnamic acid allowed the diaryl ethers to be cleaved from the resin either via saponification/transesterification or via ozonolysis. Latter offers the possibility of generating several additional compounds by simple variation of the cleavage conditions. The target substances were generally isolated in good to excellent yields and high purities.