Cation control of diastereoselectivity in iridium-catalyzed allylic substitutions. Formation of enantioenriched tertiary alcohols and thioethers by allylation of 5H-oxazol-4-ones and 5H-thiazol-4-ones.
Cation control of diastereoselectivity in iridium-catalyzed allylic substitutions. Formation of enantioenriched tertiary alcohols and thioethers by allylation of 5H-oxazol-4-ones and 5H-thiazol-4-ones.
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DOI：
10.1021/ja410650e
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发表时间：
2014-01-08
影响因子：
15
通讯作者：
Hartwig JF
中科院分区：
文献类型：
--
作者：
Chen W;Hartwig JF
我们报道了金属环铱配合物催化取代的5h -恶唑-4-酮和5h -噻唑-4-酮的高度非对映选择性烯丙基化。通过采用相应的烯醇化锌，ir催化取代5h -恶唑-4-酮的烯丙基化具有很高的非对映选择性；取代的5h -噻唑-4-酮的对映选择性需要相应的烯醇化镁来实现高的非对映选择性。取代的5h -恶唑-4-酮的烯丙基化提供了快速获得富集对映体的叔α-羟基酸衍生物的途径，这是通过mo催化的烯丙基取代无法获得的。取代5h -噻唑-4-酮的烯丙基化为合成富集对映体的叔硫醇和硫醚提供了一种新方法。观察到的阳离子效应暗示了一种新的方法来控制铁催化的烯丙基取代的非对映选择性。
We report a highly diastereo- and enantioselective allylation of substituted 5H-oxazol-4-ones and 5H-thiazol-4-ones catalyzed by the metallacyclic iridium complex. Enantioselective Ir-catalyzed allylation of substituted 5H-oxazol-4-ones occurs with high diastereoselectivity by employing the corresponding zinc enolates; enantioselective Ir-catalyzed allylation of substituted 5H-thiazol-4-ones requires the corresponding magnesium enolates to achieve high diastereoselectivity. The allylation of substituted 5H-oxazol-4-ones provides rapid access to enantioenriched tertiary α-hydroxy acid derivatives unavailable through Mo-catalyzed allylic substitution. The allylation of substituted 5H-thiazol-4-ones provides a novel method to synthesize enantioenriched tertiary thiols and thioethers. The observed cation effect implies a novel method to control the diastereoselectivity in Ir-catalyzed allylic substitution.
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影响因子：
15
作者：
Chen W;Hartwig JF
通讯作者：
Hartwig JF
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作者：
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