Functionalized imidazolidin-2-one were prepared by using an iron-catalyzed alkene oxyamination reaction. Hydroxylamine derivatives were used in this atom-economical process, and the addition of an external oxidant was not required. The conditions developed were shown to be efficient for mono-, di-, and trisubstituted double bonds, and a large scope of diamino alcohol precursors were delivered in good yields with good diastereoselectivities. The mechanistic pathway was studied and appears to involve both a fused aziridine and a carbocationic species.

A convenient and versatile procedure for the straightforward synthesis of substituted fluorenones as valuable scaffolds is described under rhodium catalysis. The present [2 + 2 + 2] cycloaddition reaction of diynes with 3-acetoxy or-3alkoxyindenones as surrogates of the highly reactive benzocyclopentynone 2π partner allows the preparation of various fluorenonetype derivatives in good yields and provides an additional and tunable process for the generation of more challenging molecules with application in pharmaceutical, polymer, and material sciences.

Chloroazaphosphatranes, the corresponding halogenophosphonium cations of the Verkade superbases, were evaluated as a new motif for halogen bonding (XB). Their modulable synthesis allowed for synthetizing chloroazaphosphatranes with various substituents on the nitrogen atoms. The binding constants determined from NMR titration experiments for Cl − , Br − , I − , AcO − , and CN − anions are comparable to those obtained with conventional iodine-based monodentate XB receptors. Remarkably, the protonated azaphosphatrane counterparts display no affinity for anions under the same conditions. The strength of the XB interaction is, to some extent, related to the basicity of the corresponding Verkade superbase. The halogen bonding abilities of this new class of halogen donor motif were also revealed by the Δδ( 31 P) NMR shift observed in CD 2 Cl 2 solution in the presence of triethylphosphine oxide (TEPO). Thus, chloroazaphosphatranes constitute a new class of halogen bond donors, expanding the repertory of XB motifs mainly based on C Ar −I bonds.