σ‐π‐Umlagerungen organischer Verbindungen der Übergangsmetalle

Absolute Asymmetric Synthesis: Viedma Ripening of [Co(bpy)3]2+ and Solvent‐Free Oxidation to [Co(bpy)3]3+

“…We speculated that if the isomerization of these diastereomeric allyl rhodium intermediates would occur faster than the subsequent addition across the imine moiety, a DYKAT should become feasible. Isomerization could either occur by a σ‐π‐σ mechanism or a β‐H elimination/readdition step 13. Once this equilibration process reaches the proper allyl isomer 4′ , which favors the addition across the imine moiety, the 1,2‐addition sets the diastereomeric and enantiomeric ratio of indanylamine 6 .…”

Rhodium‐Catalyzed Dynamic Kinetic Asymmetric Transformations of Racemic Allenes by the [3+2] Annulation of Aryl Ketimines

“…Isomerization could either occur by a s-p-s mechanism or a b-H elimination/readdition step. [13] Once this equilibration process reaches the proper allyl isomer 4', which favors the addition across the imine moiety, the 1,2-addition sets the diastereomeric and enantiomeric ratio of indanylamine 6. Along the same lines, the double bond geometry is controlled.…”