We outline a simple protocol that accesses directly unprotected secondary amines by intramolecular C–N bond forming dearomatization or aryl C–H amination. The method is dependent on the generation of a potent electrophilic aminating agent released by in situ deprotection of O-Ts activated N-Boc hydroxylamines.

In situ deprotection (TFA) of O-Ts activated N-Boc hydroxylamines triggers intramolecular aziridination of N-tethered alkenes to provide complex N-heterocyclic ring systems. Synthetic and computational studies corroborate a diastereospecific aza-Prilezhaev-type mechanism. The feasibility of related intermolecular alkene aziridinations is also demonstrated.

Diamine-mediated α-deprotonation of O-alkyl carbamates or benzoates with alkyllithium reagents, trapping of the carbanion with organoboron compounds, and 1,2-metalate rearrangement of the resulting boronate complex are the primary steps by which organoboron compounds can be stereoselectively homologated. Although the final step can be easily monitored by 11B NMR spectroscopy, the first two steps, which are typically carried out at cryogenic temperatures, are less well understood owing to the requirement for specialized analytical techniques. Investigation of these steps by in situ IR spectroscopy has provided invaluable data for optimizing the homologation reactions of organoboron compounds. Although the deprotonation of benzoates in noncoordinating solvents is faster than that in ethereal solvents, the deprotonation of carbamates shows the opposite trend, a difference that has its origin in the propensity of carbamates to form inactive parasitic complexes with the diamine-ligated alkyllithium reagent. Borylation of bulky diamine-ligated lithiated species in toluene is extremely slow, owing to the requirement for initial complexation of the oxygen atoms of the diol ligand on boron with the lithium ion prior to boron–lithium exchange. However, ethereal solvent, or very small amounts of THF, facilitate precomplexation through initial displacement of the bulky diamines coordinated to the lithium ion. Comparison of the carbonyl stretching frequencies of boronates derived from pinacol boronic esters with those derived from trialkylboranes suggests that the displaced lithium ion is residing on the pinacol oxygen atoms and the benzoate/carbamate carbonyl group, respectively, explaining, at least in part, the faster 1,2-metalate rearrangements of boronates derived from the trialkylboranes.

A C−N bond forming dearomatization protocol with broad scope is outlined. Specifically, bifunctional amino reagents are used for sequential nucleophilic and electrophilic C−N bond formations, with the latter effecting the key dearomatization step. Using this approach, γ‐arylated alcohols are converted to a wide range of differentially protected spirocyclic pyrrolidines in just two or three steps.

Dearomatization reactions allow the direct synthesis of structurally complex sp 3 -rich molecules from readily available "flat" precursors. Established dearomatization processes commonly involve the formation of new CÀ C bonds, whereas methods that enable the introduction of CÀ N bonds have received less attention. Because of the privileged position of nitrogen in drug discovery, significant recent methodological efforts have been directed towards addressing this deficiency. Consequently, a variety of new processes are now available that allow the direct preparation of sp 3 -rich amino-containing building blocks and scaffolds. This review gives an overview of CÀ N bond forming dearomatization reactions, particularly with respect to scaffold assembly processes. The discussion gives historical context, but the main focus is on selected methods that have been reported recently.