Amidate ligand design effects in zirconium-catalyzed enantioselective hydroamination of aminoalkenes

In situ generated axially chiral zirconium biphenyl amidate complexes are efficient precatalysts for the enantioselective intramolecular hydroamination of aminoalkenes, generating α-substituted pyrrolidines and piperidine with up to 74% ee. Five new chelating amide proligands and three new zirconium amidate complexes have been prepared and fully characterized in this investigation of ligand structure/catalyst function. Solid-state molecular structures of the complexes suggest that the observed moderate and highly variable enantioselectivities are a consequence of the multiple isomers accessible to this family of complexes, including a κ2-(O,O)-bonding motif. Thermal stability studies of the complexes further revealed the tendency of these complexes to undergo diastereoselective dimerization to afford homochiral dimers. These dimeric precatalysts are less efficient when used for the cyclization of aminoalkenes in comparison to their monomeric precursors. These results illustrate the variable coordination modes accessible to amidate ligands and suggest steric factors that must be considered in advanced ligand design.

Graphical abstractThe enantioselective cyclohydroamination of aminoalkenes can be achieved using zirconium amidate complexes with up to 74% ee. Tethered biphenyl amidate complexes have a variety of binding modes, resulting in sterically accessible complexes for good reactivity and enantioselectivity. Diastereoselective dimerization gives biphenyl-bridged, chiral zirconium metallacycles, decomposition products accessible under catalytic reaction conditions.Figure optionsDownload full-size imageDownload as PowerPoint slide