Recent Advances in Allylic Fluoride Synthesis

Abstract

The recent decades have witnessed considerable progress in the development of fluorinated‐building‐block strategies and direct‐fluorination techniques selectively affording allylic monofluorides and gem‐difluorides. For allylic monofluorides, high enantioselectivities were achieved, even for fluorinated tertiary carbons, with expanded substitution patterns on vinylic moieties enabling precise structural control over di‐, tri‐, and tetrasubstituted fluorides. Advances in defluorofunctionalization and direct C−H fluorination have addressed the limitations of raw materials and made these species more accessible. Additionally, considerable progress has been achieved in the related photoredox reactions, and electrochemistry has emerged as a valuable tool for allylic fluoride synthesis. This review summarizes the recent advances in the synthesis of allylic fluorides, focusing on transition metal catalysis, organocatalysis, and noncatalytic methodologies.