Blue Light-Induced 1,2-Aminochlorination of Olefins using Dichlorocarbamates

2023/12/19 by Sini Irvankoski, Michael T. Davenport, Daniel H. Ess +1 · 1 voice
Chemistry · #Catalytic C–H Functionalization Methods #Radical Photochemical Reactions #Vanadium and Halogenation Chemistry

paper · pdf · doi:10.26434/chemrxiv-2023-7t1fx

openalex publication_date 2023/12/19 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/14

Abstract

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

Discussions

• Blue light is enough to cleave the antibonding effect-weakened N-Cl bond of Cl2NBoc, facilitating mild aminochlorination of olefins. Our first method at Aalto University for constructing alkaloid scaf [bsky, 2 points, 0 comments]

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