Desulfurative Ni-Catalyzed Reductive Cross-Coupling of Benzyl Mercaptans/Mercaptoacetates with Aryl Halides

The
C–S activation and sulfur removal from native thiols
is challenging, which limits their application as feedstock materials
in organic synthesis despite their natural abundance. Herein, we introduce
a per-/polyfluoroaryl moiety, which serves as a redox-active scaffold,
into sp3-hybridized thiols to activate the C–S bond.
Using a Ni catalyst with MgBr2 as an additive, the S group
can be removed to yield an aliphatic radical that can react with an
aryl halide in a reductive cross-coupling.