Work

Chemoselective Pd-Based Dyotropic Rearrangement: Fluorocyclization and Regioselective Wacker Reaction of Homoallylic Amides

Year: 2024

Type: article

Abstract: Fluorocyclization of alkenes tethered with a pronucleophile is an efficient transformation that converts easily accessible starting materials to fluorinated heterocycles in a single step. We report herein an unprecedented Pd(II)-catalyzed oxidative domino process that transforms homoallylic amides to 5,6-dihydro-4 H -1,3-oxazines through a domino oxypalladation/Pd II –oxidation/dyotropic rearrangement/reductive elimination sequence. Three chemical bonds are created under these operationally simple conditions. Taking advantage of the facile hydrolysis of the α-fluoro tertiary alkyl ether under acidic conditions, a one-pot conversion of homoallylic amides to homologated ketones is subsequently developed, which represents a rare example of regioselective Wacker oxidation reaction of 1,1-disubstituted alkenes.

Source: Journal of the American Chemical Society

DOI: 10.1021/jacs.4c13359

Authors: Chen-Xu Liu, Qian Wang, Jieping Zhu

Institution: École Polytechnique Fédérale de Lausanne

Language: English

Topic: Fluorine in Organic Chemistry

Subfield: Pharmaceutical Science

Field: Pharmacology, Toxicology and Pharmaceutics

Domain: Life Sciences

Open Access status: green

Funders: École Polytechnique Fédérale de Lausanne, NCCR Catalysis

Award: G7142110733