A heterogeneous iridium single-atom-site catalyst for highly regioselective carbenoid O–H bond insertion

Transition-metal-catalysed carbenoid insertion of hydroxyl groups represents a robust and versatile method to forge C–O bonds. Achieving site-selective functionalization alcohols using this transformation has undoubted synthetic value but remains challenging. Here we report strategy for selective O–H that exploits an engineered heterogeneous iridium single-atom catalyst, thus providing opportunities organic transformations by merging material science catalysis. This catalytic protocol delivers excellent selectivities (up 99:1) the aliphatic over phenolic bonds, whereas analogous homogeneous Ir(ttp)COCl (ttp = 5,10,15,20-tetra-p-tolylporphyrinato), provided modest preferences. Density-functional-theory calculations suggest site-selectivity derives from lower oxidation state metal centre in catalyst its impact on absorption energies reactants. These results showcase example superior provide complementary address challenges catalysis synthesis. Supported catalysts often feature distinct reactivity when compared traditional or systems. authors introduce supported characterized remarkable selectivity versus aromatic alcohols, unlike counterpart.