Simplifying Nickel(0) Catalysis: An Air-Stable Nickel Precatalyst for the Internally Selective Benzylation of Terminal Alkenes

The synthesis and characterization of the air-stable
nickel­(II)
complex trans-(PCy2Ph)2Ni­(o-tolyl)Cl is described in conjunction with an investigation
of its use for the Mizoroki–Heck-type, room temperature, internally
selective coupling of substituted benzyl chlorides with terminal alkenes.
This reaction, which employs a terminal alkene as an alkenylmetal
equivalent, provides rapid, convergent access to substituted allylbenzene
derivatives in high yield and with regioselectivity greater than 95:5
in nearly all cases. The reaction is operationally simple, can be
carried out on the benchtop with no purification or degassing of solvents
or reagents, and requires no exclusion of air or water during setup.
Synthesis of the precatalyst is accomplished through a straightforward
procedure that employs inexpensive, commercially available reagents,
requires no purification steps, and proceeds in high yield.