title: Aryne-Mediated [2,3]-Sigmatropic Rearrangement of Tertiary Allylic Amines.
abstract: A new strategy has been established for the [2,3]-sigmatropic rearrangement of quaternary allylic ammonium ylides via in situ activation of tertiary allylic amines with arynes under mild conditions. Using 2-(trimethylsilyl)aryl triflates as aryne precursors, a range of tertiary allylic amines bearing electron-withdrawing groups underwent [2,3]-sigmatropic rearrangement to furnish structurally diverse homoallylic amines in moderate to good yields. The reaction enabled construction of quaternary stereocenters with excellent enantiopurity and functionalized cyclopropanes with extremely high diastereoselectivity.
authors.affiliation: Department of Chemistry, University of Science and Technology of China , Hefei, Anhui 230026, China.
authors.forename: Juan
authors.initials: J
authors.lastname: Zhang
authors.affiliation: Department of Chemistry, University of Science and Technology of China , Hefei, Anhui 230026, China.
authors.forename: Zhi-Xiong
authors.initials: ZX
authors.lastname: Chen
authors.affiliation: Department of Chemistry, University of Science and Technology of China , Hefei, Anhui 230026, China.
authors.forename: Ting
authors.initials: T
authors.lastname: Du
authors.affiliation: Department of Chemistry, University of Science and Technology of China , Hefei, Anhui 230026, China.
authors.forename: Bing
authors.initials: B
authors.lastname: Li
authors.affiliation: Department of Chemistry, University of Science and Technology of China , Hefei, Anhui 230026, China.
authors.forename: Yonghong
authors.initials: Y
authors.lastname: Gu
authors.affiliation: Department of Chemistry, University of Science and Technology of China , Hefei, Anhui 230026, China.
authors.forename: Shi-Kai
authors.initials: SK
authors.lastname: Tian