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Updated: Jun 8, 2025

A Two-Step Protocol for Umpolung Functionalization of Ketones Via Enolonium Species
Published on: August 16, 2018
Ultrasound-Assisted Remote Benzylic C(sp3)-H Alkylation of N-Fluoroamides with Enol Silanes
Boyi Wang1, Tianyu Lu1, Ziyu Wang1
1State Key Laboratory and Institute of Elemento-Organic Chemistry, National Engineering Research Center of Pesticide, Nankai University; College of Chemistry, Nankai University, Weijin Road 94#, Nankai District, Tianjin 300071, China.
Abstract:
We have developed an ultrasound-assisted remote benzylic C(sp3)-H alkylation of N-fluorobenzamides with enol silanes; a series of β-aryl substituted propiophenones was generated in good to high yields. This reaction represents a formal C(sp3)-C(sp3) coupling and features simplicity, high efficiency, and wide substrate scope in a multiple-step sequential process, which involves N-F homolysis, 1,5-hydrogen atom transfer, benzylic radical addition, oxidation by copper(II) salt, and removal of the trimethylsilyl group. Also, DFT theoretical calculations and Marcus theory were employed to consolidate the proposed reaction mechanism.
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