No abstract

A visible-light-driven Minisci protocol that employs an inexpensive earth-abundant metal catalyst, decacarbonyldimanganese Mn (CO) , to generate alkyl radicals from alkyl iodides has 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) . The rate-limiting step is the iodine abstraction from an alkyl iodide by Mn(CO) .

A nontoxic and inexpensive photocatalytic initiation of anti-Markovnikov hydrothiolation of olefins using visible light is reported. This method is characterized by low catalyst loading, thereby enabling a mild and selective method for radical initiation in thiol-ene reactions between a wide scope of olefins and thiols.

Avisible-light-driven Minisci protocol that employs an inexpensive earth-abundant metal catalyst, decacarbonyldimanganese Mn 2 (CO) 10 ,t og enerate alkylr adicals from alkyl iodides has been developed. This Minisci protocol is compatible with awide arrayofsensitive functional groups,including oxetanes,s ugar moieties,a zetidines,t ert-butyl carbamates (Boc-group), cyclobutanes,a nd spirocycles.T he robustness of this protocol is demonstrated on the late-stage functionalization of complex nitrogen-containing drugs.P hotophysical and DFT studies indicate al ight-initiated chain reaction mechanism propagated by CMn(CO) 5 .T he rate-limiting step is the iodine abstraction from an alkyl iodide by CMn(CO) 5 . Scheme 1. Photomediated Minisci CÀHalkylation of N-heteroarenes.