Iridium(I)-Catalyzed Decarboxylative Allylic Amidation

Significance

The first Ir(I)-catalyzed regio- and enantioselective decarboxylative allylic amidation of substituted allyl benzyl imidodicarbonates is accomplished using [Ir(cod)Cl]₂ and a phosphor­amidite ligand. The reaction has a broad scope including linear and branched alkyl, conjugated and isolated alkenyl, as well as aryl and heteroaryl substituents on the olefin. Good to excellent yields and high enantioselectivities are seen under mild reaction conditions. The synthetic utility of the products is demonstrated by allylation and subsequent ring-closing metathesis to produce a 2,5-dihydropyrrole, and by performing an intramolecular amidomercuration to produce a synthetic precursor to (+)-isosolenopsin A.