Method and Mechanistic Insights to 1,2‐Aminochlorinate Alkenes using Blue‐Light Activated Dichlorocarbamates

Blue light activation of N,N-dichlorocarbamates facilitates a direct 1,2-aminochlorination of unactivated olefins to yield 1,2-chloro-N-Cl compounds under ambient conditions. Mechanistic studies suggest that N,N-dichlorocarbamates undergo a photochemical excitation to yield a neutral nitrogen-centered radical, which rapidly reacts with olefins in an anti-Markovnikov fashion. Using this method, a range of functionally diverse substrates are successfully aminochlorinated to yield the corresponding 1,2-chloro-N-Cl compounds.