| Abstract: | An efficient, selective and recoverable catalytic system for ligand‐free aqueous Heck reactions using hydroxypropylated cyclodextrins (HPCDs) and palladium on calcium carbonate (Pd/CaCO3) is highlighted. Remarkably, stereo‐ and chemoselectivities could be tuned by the cavity size of cyclodextrins, exploiting the relevance of host‐guest interactions. UV‐Vis experiments have led to strong evidence concerning an interplay between Pd(II) and α‐HPCD, possibly ascribed to a reduction/stabilization effect of CDs. Unexpectedly, hydroarylation was the favored pathway with acrylonitrile which provided access to 3‐phenylpropionitrile derivatives without usual hydride donors. Finally, determination of soluble Pd(0/II) via AAS enabled the definition of a predominant homogeneous mechanism in which TONs over 5000 were observed. |
