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 Zvinylsilanes in high yields. Moreover, visible-light-induced manganese-catalyzed activation of the Ge−H bond for Eselective alkyne hydrogermylation is reported for the first time.

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 ah ydrogen-atom transfer (HAT) mediator and operates at room temperature with high selectivity,leading to various valuable silanols in moderate to good yields.N otably,t his electrochemical method exhibits ab road substrate scope and high functional-group compatibility,and it is applicable to late-stage functionalization of complex molecules.Preliminary mechanistic studies suggest that the reaction appears to proceed through anucleophilic substitution reaction of an electrogenerated silyl cation with H 2 O.

An approach for iodofluoroalkylation of unactivated alkynes and alkenes facilitated by an earth‐abundant and inexpensive manganese catalyst, Mn2(CO)10, is reported. This protocol employs visible light as the energy input and shows a wide substrate scope and high functional‐group compatibility. A variety of synthetically useful fluoroalkylated alkyl and alkenyl iodides can be prepared in moderate to excellent yields. The reaction features high efficiency, operational simplicity, scalability, as well as excellent chemo‐, regio‐, and E/Z selectivities.

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.

A visible-light-promoted method for generating amidyl radicals from N-fluorosulfonamides via a manganesecatalyzed N−F bond activation strategy is reported. This protocol employs a simple manganese complex, Mn 2 (CO) 10 , as the precatalyst and a cheap silane, (MeO) 3 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.