Development of New Methods for Mild Radical Coupling Reactions

The thesis describes the development of novel radical coupling transformations, visible lightinduced palladium-catalyzed alkyl Heck reaction of primary, secondary, and tertiary alkyl halides with alkenes and transition-metal- and light-free directed amination of remote unactivated C(sp3 )– H bonds of alcohols. Initially, we have introduced the first visible light-induced palladiumcatalyzed Heck reaction for a-functionalized alkyl halides with vinyl arenes/heteroarenes. This transformation utilizes a readily available catalytic system to proceed at ambient temperature and exogeneous photosensitizer-free conditions toward valuable allylic systems of diverse electronic nature. Moreover, this protocol was found applicable for challenging tertiary unactivated alkyl iodides to deliver the corresponding Heck products in excellent yields. Visible light was shown to be crucial for the success of these transformations, as the existing thermal methods failed to provide the mentioned substrates. Next, the first classical radical initiator-, transition metal-, and visible light-free auxiliary-enabled remote C−H functionalization protocol for selective g-, b-, and d-C(sp3 )−N-bond formation in aliphatic alcohols was developed. The reaction is promoted by a weak base, lithium formate, and employs readily available aryl diazonium salts to serve a double duty role as an I-atom abstracting agent and a coupling partner. The scope of obtained diazenylated alcohols is very broad, and their transformations towards amino alcohols and hydroxy ketones were accomplished with good efficiency.