Manganese-Catalyzed N-F Bond Activation for Hydroamination and Carboamination of Alkenes.

A visible-light-promoted method for generating amidyl radicals from -fluorosulfonamides via a manganese-catalyzed N-F bond activation strategy is reported. This protocol employs a simple manganese complex, Mn(CO), as the precatalyst and a cheap silane, (MeO)SiH, as both the hydrogen-atom donor and the F-atom acceptor, enabling intramolecular/intermolecular hydroaminations of alkenes, two-component carboamination of alkenes, and even three-component carboamination of alkenes. A wide range of valuable aliphatic sulfonamides can be readily prepared using these practical reactions.

Selective Electrochemical Hydrolysis of Hydrosilanes to Silanols via Anodically Generated Silyl Cations.

The first electrochemical hydrolysis of hydrosilanes to silanols under mild and neutral reaction conditions is reported. The practical protocol employs commercially available and cheap NHPI as a hydrogen-atom transfer (HAT) mediator and operates at room temperature with high selectivity, leading to various valuable silanols in moderate to good yields. Notably, this electrochemical method exhibits a broad substrate scope and high functional-group compatibility, and it is applicable to late-stage functionalization of complex molecules.

Visible-Light-Promoted Manganese-Catalyzed Atom Transfer Radical Cyclization of Unactivated Alkyl Iodides.

An expedient visible-light-promoted atom transfer radical cyclization (ATRC) reaction of unactivated alkyl iodides facilitated by earth-abundant and inexpensive manganese catalysis is described. The practical protocol shows a broad substrate scope and good functional-group tolerance, allowing for the preparation of synthetically valuable alkenyl iodides and diquinanes under simple and mild reaction conditions. Notably, the method provides a net redox-neutral strategy for ATRC reactions that avoids classic hydrogen atom transfer mechanism.

Visible-Light-Initiated Manganese-Catalyzed E-Selective Hydrosilylation and Hydrogermylation of Alkynes.

Manganese-photocatalyzed activation of the Si-H bond in silanes for the hydrosilylation of alkynes has been developed. The mild protocol operates efficiently with high regioselectivity ( anti-Markovnikov) and stereoselectivity ( Z/ E ratio ranges from 92:8 to >99:1), providing a wide range of Z-vinylsilanes in high yields. Moreover, visible-light-induced manganese-catalyzed activation of the Ge-H bond for E-selective alkyne hydrogermylation is reported for the first time.