Dearomative Dual Functionalization of Aryl Iodanes. (15th October 2019)

• Record Type: Journal Article
• Authors: Zhao, Weizhao; Huang, Xin; Zhan, Yaling; Zhang, Qifeng; Li, Dongyang; Zhang, Yage; Kong, Lichun; Peng, Bo
• Is Part Of: Angewandte Chemie. Volume 131:Number 48(2019)
• Page Start: 17370
• Page End: 17374
• Publication Date: 2019-10-15
• Subjects: Dearomatisierung -- Elektrophile Aktivierung -- Hypervalente Verbindungen -- Iod -- Sigmatrope Umlagerung; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201909019
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: Herein we describe the dearomatization of aryl iodanes through an unprecedented "rearrangement/addition" sequence. The process consists of two stages. First, a rapid [3, 3] sigmatropic rearrangement of the aryl iodane with an α‐stannyl nitrile affords a highly electrophilic dearomatized intermediate at −78 °C. A low‐temperature rearrangement then enables the unstable dearomatized species to be trapped in situ with various nucleophiles. As a consequence, the reaction not only breaks the aromaticity of the aryl iodane but also sequentially installs two different functional groups, thus resulting in a polysubstituted alicyclic product. Abstract : Platz für zwei : Der Erfolg einer neuartigen Umlagerungs‐/Additionssequenz zur Dearomatisierung von Aryliodanen basiert auf einer schnellen Umlagerung (−78 °C, 10 min), die den Abfang instabiler dearomatisierter Zwischenprodukte mit einer Reihe von Nukleophilen bei tiefer Temperatur ermöglicht (siehe Schema).