Harnessing Sulfur(VI) Fluoride Exchange Click Chemistry and Photocatalysis for Deaminative Benzylic Arylation
Deepta Chattapadhyay, Akın Aydoğan, Katarzyna Doktor, Arunava Maity, Jiun Wei Wu, Quentin Michaudel
Abstract
While being among the most common functional handles present in organic molecules, amines are a widely underutilized linchpin for C–C bond formation. To facilitate C–N bond cleavage, large activating groups are typically used but result in the generation of stoichiometric amounts of organic waste. Herein, we report an atom-economical activation of benzylic primary amines relying on the sulfur(VI) fluoride exchange (SuFEx) click chemistry and the aza -Ramberg–Bäcklund reaction. This two-step sequence allows the high-yielding generation of 1,2-dialkyldiazenes from primary amines via loss of SO 2 . Excitation of the diazenes with blue light and an Ir photocatalyst afford radical pairs upon expulsion of N 2, which can be coaxed into the formation of C(sp 3 )–C(sp 2 ) bonds upon diffusion and capture by a Ni catalyst. This arylative strategy relying on a traceless click approach was harnessed in a variety of examples, and its mechanism was investigated.