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.

芳香族 [5,5]-重排原则上是获得脱芳香族化合物的理想方案。然而，缺乏有效的[5,5]-重排阻碍了协议的进展。在本文中，我们展示了我们实验室最近开发的 [5,5]-重排的力量，用于构建一种有趣的脱芳族锍物质，该物质具有多种独特的反应性，可进行亲核 1,2- 和 1,4- 加成和环化，从而实现易于获得的芳基亚砜的脱芳族双官能团和三官能团化。令人印象深刻的是，脱芳构化产物可以很容易地转化为脱硫的环己烯酮、萘酮、双环环己二烯酮和多取代苯。机理研究揭示了关键中间体和显着的化学、