A Hafnium-Based Metal-Organic Framework as a Nature Inspired Tandem Reaction Catalyst

Beyzavi, M. H.; Vermeulen, N. A.; Howarth, A. J.; Tussupbayev, S.; League, A. B.; Schweitzer, N. M.; Gallagher, J. R.; Platero-Prats, A. E.; Hafezi, N.; Sarjeant, A. A.; Miller, J. T.; Chapman, K. W.; Stoddart, J. F.; Cramer, C. J.; Hupp, J. T.; Farha, O. K.
J. Am. Chem. Soc. 2015, 137, 13624 (doi:10.1021/jacs.5b08440).

Tandem catalytic systems, often inspired by biological systems, offer many advantages in the formation of highly functionalized small molecules. Herein, a new MOF with porphyrinic struts and Hf₆ nodes is reported. This MOF demonstrates catalytic efficacy in the tandem oxidation and functionalization of styrene utilizing molecular oxygen as a terminal oxidant. The product, a protected 1,2-aminoalcohol, is formed selectively and with high efficiency using this recyclable heterogeneous catalyst. Significantly, the unusual regioselective transformation occurs only when a Fe-decorated Hf₆-node and the Fe-porphyrin strut work in concert. This report is an example of concurrent orthogonal tandem catalysis.