Tuning the Porphyrin Building Block in Self‐Assembled Cages for Branched‐Selective Hydroformylation of Propene

Unprecedented regioselectivity to the branched aldehyde product in the hydroformylation of propene was attained on embedding a rhodium complex in supramolecular assembly L2, formed by coordination‐driven self‐assembly of tris(meta‐pyridyl)phosphine and zinc(II) porpholactone. The design of cage L2 is based on the ligand‐template approach, in which the ligand acts as a template for cage formation. Previously, first‐generation cage L1, in which zinc(II) porphyrin units were utilized instead of porpholactones, was reported. Binding studies demonstrate that the association constant for the formation of second‐generation cage L2 is nearly an order of magnitude higher than that of L1. This strengthened binding allows cage L2 to remain intact in polar and industrially relevant solvents. As a consequence, the unprecedented regioselectivity for branched aldehyde products can be maintained in polar and coordinating solvents by using the second‐generation assembly.