Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Zhejiang Normal University, Jinhua, China.
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian, China.
Nat Commun. 2022 Aug 11;13(1):4719. doi: 10.1038/s41467-022-32426-6.
Aromatic [5,5]-rearrangement can in principle be an ideal protocol to access dearomative compounds. However, the lack of competent [5,5]-rearrangement impedes the advance of the protocol. In this Article, we showcase the power of [5,5]-rearrangement recently developed in our laboratory for constructing an intriguing dearomative sulfonium specie which features versatile and unique reactivities to perform nucleophilic 1,2- and 1,4-addition and cyclization, thus achieving dearomative di- and trifunctionalization of easily accessible aryl sulfoxides. Impressively, the dearomatization products can be readily converted to sulfur-removed cyclohexenones, naphthalenones, bicyclic cyclohexadienones, and multi-substituted benzenes. Mechanistic studies shed light on the key intermediates and the remarkable chemo-, regio- and stereoselectivities of the reactions.
[5,5]-重排原则上可以成为一种理想的方法来获得去芳构化合物。然而，缺乏有效的[5,5]-重排阻碍了该方法的进展。在本文中，我们展示了我们实验室最近开发的[5,5]-重排的强大功能，用于构建一种有趣的去芳构化的锍物种，该物种具有多种多样且独特的反应性，可进行亲核 1,2-和 1,4-加成以及环化，从而实现易于获得的芳基砜的去芳构化双官能化和三官能化。令人印象深刻的是，去芳构化产物可以很容易地转化为硫去除的环己烯酮、萘满酮、双环环己二烯酮和多取代苯。机理研究揭示了反应的关键中间体以及显著的化学、区域和立体选择性。
