Novel visible-light promoted iridium-photoredox and nickel-catalyzed methods for C-S and C-N bonds formation have been developed. These protocols are robust, mild and have broad substrates scope. Photophysical and spectroscopic studies were used to probe the mechanisms of these new reactions. These C-S and C-N bond-forming reactions proceed through thiyl and aminyl radicals respectively. A photoredox Minisci protocol that employs an inexpensive earth-abundant metal catalyst, decacarbonyldimanganese Mn2(CO)10 to generate alkyl radicals from primary, secondary and tertiary alkyl iodides has also been developed. This Minisci protocol is compatible with a wide array of sensitive functional groups, including oxetanes, sugar moieties, azetidines, tert-butyl carbamates (Boc-group), cyclobutanes, and spirocycles. The robustness of this protocol is demonstrated on the late-stage functionalization of complex nitrogen-containing drugs. Photophysical and DFT studies indicate a light-initiated chain reaction mechanism propagated by Mn(CO)5 radical. The rate limiting step is the iodine abstraction from an alkyl iodide by Mn(CO)5 radical.

Visible-light promoted C-S, C-N, and C-C bond-forming reactions: Applications and mechanistic studies

255th National Meeting (2018)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.