Dearomative Dual Functionalization of Aryl Iodanes

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.

Dearomatization of aryl sulfoxides: a switch between mono- and dual-difluoroalkylation

“…It is worth mentioning that, in our recent studies, ortho, ortho 0 -dimethyl phenyl iodine(III) diacetate was also found to be suitable for a related dearomative rearrangement process. 16 To our surprise, aside from the expected 3a, the reaction also produced a small amount of dual-diuoroalkylated product 4a (15%) which showed sufficient nucleophilicity of DFESE not only for the rearrangement with sulfoxide but also for the capture of the in situ-formed dearomatized intermediate. Notably, the reaction is unusually sensitive to the polarity of the solvent since slightly tuning the ratio of the combined solvents could exert a signicant inuence on the reaction outcome (entries 2-5).…”

The Power of Iodane‐Guided C−H Coupling: A Group‐Transfer Strategy in Which a Halogen Works for Its Money

“…The method is based on intercepting the cationic Friedel-Crafts-type intermediates, arising immediately after the rearrangement (as seen in Scheme 29 right), with incoming H-or C-based nucleophiles. [46] Besides the methods synthetic usefulness, this work provides one of the earliest experimental evidence for a time lag between the rearrangement and rearomatization steps in this class of mechanisms. Finally, the same group also reported a diastereoselective variant of the a-arylation of aliphatic carboxylic acids masked in the form of chiral oxazolines.…”

Morita-Baylis-Hillman Reaction Inspired [3,3]-Rearrangement of Aryl Iodanes with α,β-Unsaturated Oxazolines

“…[5][6] The subsequent [3,3]-rearrangement occurs spontaneously leading to synthetically appealing ortho-functionalized aryl iodides. In the past three decades, an array of nucleophiles such as allyl/propargyl silanes, [7][8][9][10][11][12][13][14] carbonyl compounds, 15,16 phenols, 17 α-stannyl nitriles, [18][19][20][21] and enol silyl ethers 22 have been found to be suitable for the rearrangement process. Despite the progresses made, the reaction scope of carbonyl nucleophiles is limited to structurally de ned carbonyl compounds ( Fig.…”