Aryne triggered [2,3]-sigmatropic rearrangement of allyl and propargyl thioethers

Abstract

An efficient protocol for [2,3]-sigmatropic rearrangement of allyl and propargyl thioethers is reported.

o-Silylaryl Triflates: A Journey of Kobayashi Aryne Precursors

“…Beside ammonium ylides, sulfonium ylides could also be facilely generated from arynes and thioethers upon S-arylation and deprotonation. In 2017, the groups of Biju and Tan/Xu independently reported an aryne-induced [2,3] Stevens rearrangement with allylthioethers 9-115 , affording functionalized β-keto arylthioethers 9-116 and 9-117 in modest to high yields with high functional group tolerance (Scheme ). In the study carried out by Tan, Xu, and co-workers, propargyl thioethers were also examined …”

Recent advance in sulfur ylide and sulfonium salts chemistry

“…排反应引起了广泛关注 [11] . 在前人工作以及苯炔引 发 的 基 于 氮 叶 立 德 中 间 体 的 叔 胺 重 排 反 应 基 础 上 [12,13] , 本课题组 [14] 报道了一类苯炔引发的烯丙基 硫醚的 [2,3] 印度Biju课题组 [15] 以及重庆大学贺耘课题组 [16] [27] . 近年来, 基于金属卡宾和硫醚的重排反 应愈发引起了科学家的重视, 在不对称催化以及水 相合成等方面已有突破性的进展.…”

Regioselective Synthesis of 2‐(Trifluoromethyl)‐3‐ethoxycarbonyl‐4‐(2‐oxo‐2‐arylethyl)‐4H‐chromene Derivatives by [3, 3] Sigmatropic Rearrangement

“…Thereafter, the BF 3 . OEt 2 drives nucleophilic addition on carbocation of acetylene by elimination of BF 3 .OEt 2 and forms intermediate D which by [3, 3] sigmatropic rearrangement, results 4‐(2‐oxo‐2‐phenylethyl)‐2‐(trifluoro methyl)‐4 H ‐chromene‐3‐carboxylate 3 a .…”