MOF-808 as a Highly Active Catalyst for the Diastereoselective Reduction of Substituted Cyclohexanones

Abstract

Zr-containing MOF-808 is an excellent heterogeneous catalyst for the diastereoselective Meerwein–Ponndorf–Verley reduction of substituted cyclohexanones. The presence of substituents at the 2 or 3 position of the cyclohexanone ring strongly drives the reaction towards the formation of one of the two possible isomers. For 3-methyl cyclohexanone, the available space inside the MOF pores allows the formation of the bulkier transition state leading to the thermodynamically stable 3-cis-cyclohexanol. For 2-methyl cyclohexanone, the reaction rate is much slower and the final diastereoselectivity depends on the size of the alcohol used. Finally, reduction of 2-phenyl cyclohexanone is considerable faster over MOF-808 than for any other catalyst reported so far. The large size of the phenyl favors the selective formation (up to 94% selectivity) of the cis-alcohol, which goes through a less hindered transition state.