Designing the secondary coordination sphere in small-molecule catalysis

The application of secondary-sphere interactions in catalysis was inspired by the hierarchical arrangement of the microenvironment of metalloprotein active sites and has been adopted mainly in organometallic catalysis. The study of such interactions has enabled the deliberate orientation of reaction components, leading to control over reactivity and selectivity by design. Although not as common, such interaction can play a decisive role in organocatalysis. Herein, we present several examples of small-molecule organometallic- and organocatalysis, highlighting the advantages offered by carefully designing the secondary sphere. 1 Introduction 2 Secondary-Sphere Design in Organometallic Catalysis 3 Secondary-Sphere Modification in Organocatalysis 4 Using Statistical Analysis to Systematically Tune and Probe Secondary-Sphere Interactions 5 Conclusion.