Synthesis and Structures of Novel Chiral Cyclic Hypervalent Iodine(III) Reagents for Metal‐Free Ligand‐Transfer Reactions

ABSTRACT

The preparation of novel chiral λ ³ ‐iodane reagents bearing transferable halogen‐, oxygen‐ or carbon‐based ligands is described. Among these hypervalent iodine(III)‐based compounds are (i) the first chiral bis(cyano‐λ ³ ‐iodane), whose bis(benziodazolone) structure is derived from an enantiopure cyclohexyldiamine‐based bis(amidoiodoarene), and (ii) the two first chiral benziodoxolones bearing a carbon‐based ligand (i.e., cyano and trifluoromethyl groups) together with a lactate moiety ortho ‐positioned to the iodine(III) atom. The proposed iodine‐containing heterocyclic structures of these new λ ³ ‐iodanes are supported by x‐ray diffraction analyses and DFT calculations. Their capacity to transfer their ligand(s) in an asymmetric fashion to different substrates (i.e., β‐ketoesters, naphthols, and oxindoles) was also examined.