Aromatic Claisen Rearrangements of Benzyl Ketene Acetals: Conversion of Benzylic Alcohols to (
<i>ortho</i>
‐Tolyl)acetates
作者:Jed M. Burns、Elizabeth H. Krenske、Ross P. McGeary
DOI:10.1002/ejoc.201601354
日期:2017.1.10
Claisen rearrangements of benzyl vinyl ethers are much less facile than those of aliphatic allyl vinyl ethers, and their synthetic utility has remained relatively unexplored. A one-pot procedure is reported for the generation and Claisen rearrangement of benzyl vinyl ethers that contain an activating α-alkoxy substituent on the vinyl group. A [3,3]-sigmatropic mechanism was supported by trapping of the
苄基乙烯基醚的克莱森重排远不如脂肪族烯丙基乙烯基醚的克莱森重排容易,并且它们的合成效用仍然相对未开发。据报道,一锅法用于生成和克莱森重排苄基乙烯基醚,在乙烯基上含有活化的 α-烷氧基取代基。通过在分子内 Alder-ene 反应中捕获中间体异甲苯来支持 [3,3]-σ 机制。