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.

本文报道了配体参与策略在铱催化亚胺基转移至炔烃反应中的应用。基于Cp*Ir(III)(κ2-N,O-螯合物)与炔基二噁唑酮的化学计量[3+2]环加成反应，本研究首次以[Cp*IrCl₂]₂为预催化剂、NaX盐（X=Cl或Br）作为实用卤源，开发了催化卤代酰胺化反应，可获得具有优异立体选择性、合成用途广泛的Z-(卤乙烯基)内酰胺。