No abstract

Easy recognition and numerical description of isostructurality; how different the similar structures can be; supramolecular aspects of isostructurality.

An exo-selective catalytic Diels–Alder reaction was developed using a Lewis acid catalyst with size-exclusion structural design. Exploiting the steric effect, especially the steric attraction, the Lewis acid catalyst was able to reroute the reaction along a higher-energy pathway. The experimental findings were also supported by theoretical calculations. This catalyst development allows an easy and practical access to highly complex and pharmaceutically relevant compounds.

The reductive Ireland–Claisen rearrangement through borane‐mediated hydrosilylation is reported. The method employs a borane catalyst with a special structural design and affords access to synthetically relevant products with high diastereoselectivity. Depending on electronic and structural parameters, the reaction can be coupled with a 1,3‐allylic shift, thus the valence isomer of the Ireland–Claisen product is formed.