Asymmetric Synthesis of Chiral Sulfimides through the <i>O</i> ‐Alkylation of Enantioenriched Sulfinamides and Addition of Carbon Nucleophiles
Asymmetric Synthesis of Chiral Sulfimides through the <i>O</i> ‐Alkylation of Enantioenriched Sulfinamides and Addition of Carbon Nucleophiles
复制标题
通过对映体富集的亚磺酰胺的 <i>O</i> -烷基化和碳亲核试剂的加成不对称合成手性磺酰亚胺
DOI：
10.1002/anie.202300637
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发表时间：
2023
期刊：
影响因子：
--
通讯作者：
Kano Taichi
中科院分区：
文献类型：
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作者：
Tsuzuki Saori;Kano Taichi
手性硫酰亚胺，亚砜的氮杂类似物，是有机合成和药物化学中有价值的化合物。在此，我们报道了一种从容易获得的对映体富集的亚磺酰胺制备手性硫酰亚胺的有效方法。该方法的关键步骤是对映体富集的亚磺酰胺的立体特异性氧选择性烷基化，其通过使用异丙基碘、K2CO3和DMPU来完成。在简单的条件下，通过格氏试剂的亲核加成将所得手性亚磺酰亚胺酯转化为手性硫酰亚胺。这种转化使得能够获得具有两个相似碳取代基的对映体富集的二芳基或二烷基硫酰亚胺，这是难以通过以前的方法合成的。
Chiral sulfimides, the aza‐analogues of sulfoxides, are valuable compounds in organic synthesis and medicinal chemistry. Herein, we report an efficient method for preparing chiral sulfimides from easily available enantioenriched sulfinamides. The key step of this method is a stereospecific oxygen‐selective alkylation of enantioenriched sulfinamides, which is accomplished by using isopropyl iodide, K2CO3, and DMPU. The resulting chiral sulfinimidate esters are transformed to chiral sulfimides by the nucleophilic addition of the Grignard reagents under simple conditions. This transformation enables access to the enantioenriched diaryl or dialkyl sulfimides bearing two similar carbon substituents, which are difficult to synthesize by previous methods.