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Fluorine incorporation by concomitant fluoroalkyl radical addition to alkene or alkyne and functional group migration (FGM) represents an ingenious and robust strategy for the synthesis of structurally diverse fluorinated compounds. This account gives an overview of related studies in our group, in which three main reaction modes are discussed: 1) radical fluoroalkylative difunctionalization of unactivated alkenes via intramolecular FGM; 2) alkene difunctionalization by docking‐migration process using fluoroalkyl‐containing bifunctional reagents; 3) incorporation of fluoroalkyl group into C(sp3)−H bond via consecutive hydrogen atom transfer (HAT) and FGM. Relying on these methods, a variety of trifluoromethylation and di‐/mono‐fluoroalkylation reactions along with the migration of cyano, heteroaryl, oximino, formyl, alkynyl, and alkenyl groups have been accomplished under mild conditions. [ABSTRACT FROM AUTHOR]

Heteroarenes are important units in organic chemistry and are ubiquitous in natural products, pharmaceuticals, and numerous artificial molecules. Despite great efforts devoted to accessing heteroarenes, the development of new methods to efficiently produce heteroarenes remains a long-term interest. Recently, the strategy of radical-mediated heteroaryl migration has supplied a robust toolkit for the synthesis of a diversity of heteroaryl-containing compounds. This Account summarizes our recent achievements in this field and provides insight into the incorporation of heteroarenes into organic skeletons. 1 Introduction 2 Radical-Mediated Heteroarylation of Alkanes and Alkenes via Intramolecular Heteroaryl Migration 2.1 C(sp3)–H Heteroarylation via Intramolecular Heteroaryl Migration 2.2 Difunctionalization of Alkenes via Intramolecular Heteroaryl Migration 3 Intermolecular Difunctionalization of Alkenes via 'Docking-Migration' Strategy 3.1 Sulfone-Based Bifunctional Reagents for Difunctionalization of Alkenes by Docking Migration 3.2 Sulfone-Based Reagents for the Synthesis of N-Fused Heteroarenes by Docking Migration 3.3 Tertiary Alcohol Based Bifunctional Reagents for Difunctionalization of Alkenes by Docking Migration 3.4 Diaryl Ether Based Bifunctional Reagents for Difunctionalization of Alkenes by Docking Migration 3.5 Conclusion [ABSTRACT FROM AUTHOR]

Radical‐mediated difunctionalization of alkenes provides a promising approach to introduce one alkenyl or alkynyl group to target compounds. However, simultaneous installation of two unsaturated C−C bonds via alkene difunctionalization remains elusive, attributable to the high instability and transient lifetimes of alkenyl and alkynyl radicals. Herein, we report the photocatalytic 1,2‐alkynylalkenylation and 1,2‐enynylalkenylation of alkenes for the first time, triggered by the intermolecular addition of a stabilized allenyl radical to an alkene. A portfolio of strategically designed, easily accessible dual‐function reagents are applied to a radical docking‐migration cascade. The protocol has broad substrate scope and efficiently increases the degree of unsaturation. [ABSTRACT FROM AUTHOR]

We report a new reaction mode involving functional group migration, which is applied to the radical-mediated remote desaturation of hexenenitriles. The reaction proceeds through consecutive alkene sulfonylation, intramolecular cyano migration, and single-electron oxidation of benzyl radical to cation followed by deprotonation, leading to a variety of densely functionalized alkenes. The protocol features mild photocatalytic conditions, broad functional group tolerance, and high product diversity. [Display omitted] [ABSTRACT FROM AUTHOR]