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Radical-mediated controllable difunctionalization of alkenes provides a powerful tool for the manipulation of olefins and has become a hot topic recently. In general, however, the scope of alkene is largely restricted to the activated alkenes. The development of a general strategy for the functionalization of unactivated alkenes is desired, yet remains challenging. In this review, we have summarized the recent advances in the strategy of intramolecularly distal migration of functional groups which has been efficiently applied in the radical-mediated difunctionalization of unactivated alkenes. A portfolio of functionalities including aryl, cyano, heteroaryl, imino, carbonyl, alkynyl, and alkenyl groups showcase the migratory aptitude. [ABSTRACT FROM AUTHOR]

Abstract An efficient visible-light photocatalytic protocol for the vicinal heteroarylsulfonylation and oximinosulfonylation of unactivated olefins is described. The addition of sulfonyl radicals to alkenes triggers the intramolecular migration of remote heteroaryl and oximino groups via C C bond cleavage. The transformation features a good functional group tolerance and a broad substrate scope. A variety of valuable heteroaryl- and oximino-substituted alkyl sulfones are obtained under mild conditions in synthetically useful yields. Graphical abstract Image 1 [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]

• Novel approach for radical-mediated trifluoromethylative aminocarbonylation of unactivated olefins. • The reaction features mild conditions, good functional group tolerance, and broad substrate scope. • The CF 3 -functionalized γ-lactam products are synthetically valuable. An efficient approach for the synthesis of γ-lactams through radical-mediated trifluoromethylative aminocarbonylation of unactivated olefins is described. The transformation is initiated by the addition of an external CF 3 radical to alkene followed by interception with intramolecular cyanamide. This protocol provides a useful method to furnish the synthetically valuable CF 3 -functionalized γ-lactams. [ABSTRACT FROM AUTHOR]