A copper‐catalyzed three‐component coupling of allenes, bis(pinacolato)diboron, and imines allows regio‐, chemo‐, and diastereoselective assembly of branched α,β‐substituted‐γ‐boryl homoallylic amines, that is, products bearing versatile amino, alkenyl, and borane functionality. Alternatively, convenient oxidative workup allows access to α‐substituted‐β‐amino ketones. A computational study has been used to probe the stereochemical course of the cross‐coupling.

A highly enantio‐ and diastereoselective copper‐catalyzed three‐component coupling affords the first general synthesis of homoallylic amines bearing adjacent stereocenters from achiral starting materials. The method utilizes a commercially available NHC ligand and copper source, operates at ambient temperature, couples readily available simple imines, allenes, and diboranes, and yields high‐value homoallylic amines that exhibit versatile amino, alkenyl, and boryl units.

The first asymmetric silylation of unsaturated lactams and amides using Cu(I)-NHC catalysts and PhMe2SiBpin has been accomplished. The method has been exploited in an expedient asymmetric synthesis of the (R)-enantiomer of the nootropic drug oxiracetam.

Axially chiral C−N compounds are an emerging but scarcely investigated class of stereogenic molecules with potential applications as biologically active scaffolds and chiral ligands. The synthesis of these compounds is extremely challenging, and in particular, no metal-catalyzed asymmetric, intermolecular C−N coupling has been previously reported. Herein we disclose an intermolecular atropselective C−N coupling, occurring with excellent stereoselectivity. This Cucatalyzed transformation is based on the use of highly active coupling partners (i.e., chiral iodanes bearing a very cheap and traceless sulfoxide auxiliary). Use of such original ortho-sulfoxide iodanes enables this unprecedented coupling to occur at room temperature, guaranteeing high atropselectivity and atropselectivity of the coupling products under reaction conditions. Because of extensive possible postmodifications of the optically pure products, a panel of C−N axially chiral scaffolds can now be accessed.