Alkenes are ubiquitous in natural products and are extensively used as synthetic feedstocks in multiple fields including organic synthesis, medicinal chemistry, and materials science. Radical-mediated difunctionalization of alkenes provides a powerful tactic for alkene utilization. Despite the considerable progress made in the past several decades, state-of-the-art methods are highly dependent upon activated alkenes in which a proximal group with a π-electron system (e.g., aryl, carbonyl, and heteroatom) is requisite to stabilize the nascent alkyl radical intermediate via p-π conjugation or p orbitals of the heteroatom. In contrast, the transformation of unactivated alkenes, such as aliphatic alkenes, remains challenging.To overcome this obstacle, we have recently disclosed the strategy of intramolecular distal functional group migration (FGM), which has been efficiently applied in radical difunctionalization of unactivated alkenes. A portfolio of functional groups, such as cyano, heteroaryl, oximino, formyl, and alkynyl groups, showcase the excellent migratory aptitude. Mechanistically, after the addition of an extrinsic radical to the alkene, the newly formed active alkyl radical is rapidly captured by the intramolecular migratory group to generate a cyclic intermediate. Subsequent cleavage of the cyclic C-C bond of the intermediate leads to the functionalized product through the FGM process. Based on the strategy of FGM, a set of elusive difunctionalizations of unactivated alkenes have been accomplished (Part A).Alongside this research, an upgraded highly efficient synthetic strategy, "dock-migration," is created for intermolecular difunctionalization of alkenes. A diversity of sulfone-based dual-function reagents are developed. The intermolecular transformation is initiated by docking the dual-function reagent to the alkene, followed by intramolecular migration of the functional group. Compared to the original FGM protocol, the scope of alkenes is significantly extended from the strategically placed tertiary alcohol-substituted alkenes to general alkenes. Both activated and unactivated alkenes are well tolerated. By this approach, radical-mediated fluoroalkylheteroarylation, fluoroalkylalkynylation, and alkylation of alkenes have been achieved (Part B).Direct elaboration of C-H bonds into the targeted functional groups represents one of the most ideal and straightforward methods for molecular functionalization. The FGM strategy proves to be an ingenious tool for radical-mediated functionalization of remote unactivated C(sp3)-H bonds. Based on the FGM process, we have accomplished: (a) remote C(sp3)-H heteroarylation and cyanation of unprotected alcohols via the cascade of alkoxy radical-enabled hydrogen atom transfer (HAT) and intramolecular functional group (e.g., heteroaryl, cyano) migration, and (b) distal C(sp3)-H vinylation of propargylic alcohols through consecutive alkenyl radical-promoted HAT process and subsequent alkenyl migration (Part C).