通过芳基亚砜与烯丙基腈的组装进行的选择性[5,5]-σ迁移重排反应。
Selective [5,5]-Sigmatropic Rearrangement by Assembly of Aryl Sulfoxides with Allyl Nitriles.
作者信息
Zhang Lei, He Jia-Ni, Liang Yuchen, Hu Mengjie, Shang Li, Huang Xin, Kong Lichun, Wang Zhi-Xiang, Peng Bo
机构信息
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Zhejiang Normal University, Jinhua, 321004, China.
School of Chemistry and Chemical Engineering, University of the Chinese Academy of Sciences, Beijing, 100049, China.
出版信息
Angew Chem Int Ed Engl. 2019 Apr 8;58(16):5316-5320. doi: 10.1002/anie.201900434. Epub 2019 Mar 13.
Aromatic [5,5]-sigmatropic rearrangement is an appealing protocol for accessing 1,4-substituted arenes. However, such a protocol has not been well utilized in organic synthesis because of the difficulties in the synthesis of the substrates, selectivity issues, and limited substrate scope. Described herein is a new [5,5]-sigmatropic reaction utilizing readily available aryl sulfoxides and allyl nitriles. This reaction features mild reaction conditions, high chemo- and regioselectivity, excellent functional-group compatibility, and broad substrate scope. Computational studies suggest that the success of the reaction can be attributed to the selective electrophilic assembly of the rearrangement precursors, in which a linear -C=C=N- linkage favors [5,5]-sigmatropic rearrangement over the competitive [3,3]-sigmatropic rearrangement.
芳香族[5,5] - 西格玛重排是合成1,4 - 二取代芳烃的一种有吸引力的方法。然而，由于底物合成困难、选择性问题以及底物范围有限，这种方法在有机合成中尚未得到充分利用。本文描述了一种利用易于获得的芳基亚砜和烯丙基腈的新型[5,5] - 西格玛重排反应。该反应具有反应条件温和、化学和区域选择性高、官能团兼容性好以及底物范围广等特点。计算研究表明，该反应的成功可归因于重排前体的选择性亲电组装，其中线性-C = C = N-键比竞争性的[3,3] - 西格玛重排更有利于[5,5] - 西格玛重排。
Zotero 插件