Ir(III)-Catalyzed Stereoselective Haloamidation of Alkynes Enabled by Ligand Participation

Described herein is the application
of a strategy of ligand participation
for the Ir-catalyzed imido transfer into alkynes. On the basis of
a stoichiometric [3 + 2] cycloaddition of Cp*Ir­(III)­(κ2-N,O-chelate) with alkynyl dioxazolone,
a catalytic haloamidation was developed for the first time by employing
[Cp*IrCl2]2 precatalyst and NaX salts (X = Cl
or Br) as practical halide sources to furnish synthetically versatile Z-(halovinyl)­lactams with excellent stereoselectivity.