The inertness of chloroalkanes has precluded them as coupling partners for cross‐coupling reactions. Herein we disclose a general strategy for the activation of inert alkyl chlorides through photoredox catalysis and their use as coupling partners with alkenes. The catalytic system is formed by [Ni(OTf)(Py2Tstacn)](OTf) (1Ni), which is responsible for the Csp3−Cl bond activation, and [Ir(NMe2bpy)(ppy)2]PF6, (PCIrNMe2), which is the photoredox catalyst. Combined experimental and theoretical studies show an in situ photogenerated NiI intermediate ([Ni(Py2Tstacn)]+) which is catalytically competent for the Csp3−Cl bond cleavage via a SN2 mechanism for primary alkyl chlorides, forming carbon‐centered free radicals, which react with the olefin leading to the formation of the Csp3−Csp3 bond. These results suggest inert alkyl chlorides can be electrophiles for developing new intermolecular strategies in which low‐valent aminopyridine nickel complexes act as key catalytic species.

A catalytic system based on earth-abundant elements that efficiently hydrogenates aryl olefins using visible light as driving-force and H2O as the sole hydrogen atom source is reported. The catalytic system...

The inertness of chloroalkanes has precluded them as coupling partners for cross-coupling reactions. Herein we disclose a general strategy for the activation of inert alkyl chlorides through photoredox catalysis and their use as coupling partners with alkenes. The catalytic system is formed by [Ni(OTf)(Py 2 Ts tacn)](OTf) (1 Ni ), which is responsible for the Csp 3 À Cl bond activation, and [Ir( NMe2 bpy)(ppy) 2 ]PF 6, (PC Ir NMe2 ), which is the photoredox catalyst. Combined experimental and theoretical studies show an in situ photogenerated Ni I intermediate ([Ni(Py 2Ts tacn)] + ) which is catalytically competent for the Csp 3 À Cl bond cleavage via a S N 2 mechanism for primary alkyl chlorides, forming carboncentered free radicals, which react with the olefin leading to the formation of the Csp 3 À Csp 3 bond. These results suggest inert alkyl chlorides can be electrophiles for developing new intermolecular strategies in which low-valent aminopyridine nickel complexes act as key catalytic species.

Photocatalysis The photoredox activation of inert chloroalkanes for cross‐coupling reactions with olefins is presented by Julio Lloret‐Fillol et al. in their Research Article (e202114365). The reaction is characterized by a broad functional group tolerance and proceeds under mild conditions.