Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Zhejiang Normal University, Jinhua 321004, China.
School of Chemical Sciences, University of the Chinese Academy of Sciences, Beijing 100049, China.
J Am Chem Soc. 2020 Apr 15;142(15):6884-6890. doi: 10.1021/jacs.0c00783. Epub 2020 Mar 19.
Here we describe an asymmetric [3,3]-sigmatropic rearrangement of aryl iodanes that enables the enantioselective α-arylation of chiral 2-oxazolines, thereby producing valuable chiral α-aryl carbonyl compounds. The success of this protocol hinges on the selective assembly of aryl iodanes with 2-oxazolines and the smooth deprotonation of the in situ-generated iodonium-imine species. The nearly neutral and mild conditions of the reaction allow it to tolerate a wide variety of functional groups. Moreover, the remaining iodine atom in the products not only provides a versatile platform for further elaboration of such molecules but also supplies the asymmetric hypervalent iodine chemistry with a new class of chiral scaffolds.
在这里，我们描述了芳基碘烷的不对称 [3,3]-σ重排，该重排能够实现手性 2-恶唑啉的对映选择性α-芳基化，从而生成有价值的手性 α-芳基羰基化合物。该方案的成功取决于芳基碘烷与 2-恶唑啉的选择性组装以及原位生成的碘翁-亚胺物种的顺利脱质子化。反应的近中性和温和条件允许其容忍各种官能团。此外，产物中剩余的碘原子不仅为进一步修饰此类分子提供了一个多功能平台，而且为不对称高价碘化学提供了一类新的手性支架。
