Chemical processes proceed much faster and more selectively in the presence of appropriate catalysts, and as such the field of catalysis is of key importance for the chemical industry, especially in light of sustainable chemistry. Enzymes, the natural catalysts, are generally orders of magnitude more selective than synthetic catalysts and a major difference is that they take advantage of well-defined cavities around the active site to steer the selectivity of a reaction via the second coordination sphere. Here we demonstrate that such a strategy also applies for a rhodium catalyst; when used in the hydroformylation of internal alkenes, the selectivity of the product formed is steered solely by changing the cavity surrounding the metal complex. Detailed studies reveal that the origin of the capsule-controlled selectivity is the capsule reorganization energy, that is, the high energy required to accommodate the hydride migration transition state, which leads to the minor product.

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