The Front Cover shows the first use of the new asymmetric CuAAC click reaction to induce planar stereogenicity. Stereodifferentiation in asymmetric induction (in the first CuAAC) and kinetic resolution (in the second CuAAC) are both influenced by (R,R)‐Ph‐Pybox ligands on copper and so both contribute to the observed ees of the chiral monotriazole products. We acknowledge Daniel Starling for graphic design and QuteMol for images of space filling models of Ph‐Pybox which were generated from xyz data obtained by DFT calculations by the authors using Gaussian. More information can be found in the Full Paper by G. R. Stephenson et al.

The Front Cover shows the first use of the new asymmetric CuAAC click reaction to induce planar stereogenicity. Stereodifferentiation in asymmetric induction (in the first CuAAC) and kinetic resolution (in the second CuAAC) are both influenced by (R,R)‐Ph‐Pybox ligands on copper and so both contribute to the observed ees of the chiral monotriazole products. We acknowledge Daniel Starling for graphic design and QuteMol for images of space filling models of Ph‐Pybox which were generated from xyz data obtained by DFT calculations by the authors using Gaussian. More information can be found in the Full Paper by G. R. Stephenson et al.

A new copper catalysed desymmetrisation reaction of bisalkynyl ferrocenecarboxylic acids using (R,R)-Ph-Pybox results in the first asymmetric synthesis of planar chiral pseudo-isocoumarins in up to 64 % enantiomeric excess and up to 99 % yield with complete regioselectivity. Tri-functionalised planar chiral ferrocenes are synthesised in five steps from commercially available materials, without the need for traditional directing group chemistry via an easily diversified route exploiting the double Sonogashira coupling reaction. The absolute configuration of the chiral heterocycles is proven by chemical correlation and circular dichroism spectroscopy giving the asymmetric reaction synthetic utility and opening the way for the rational extension of this method to produce bioactive isocoumarin-fused ferrocene derivatives.