A Green Alternative for the Direct Aerobic Iodination of Arenes Using Molecular Iodine and a POM@MOF Catalyst.

Iodoarenes are important precursors for fine chemicals and pharmaceuticals. The direct iodination of arenes using molecular iodine (I 2 ) has emerged as an attractive green synthesis method. Most of the direct iodination protocols are still homogeneous systems that require harsh conditions and use or produce toxic products. We report a new heterogeneous catalytic route for the direct aerobic iodination of arenes under mild conditions using a PMoV 2 polyoxometalate (POM) embedded in the metal-organic framework (MOF) MIL-101 (PMoV 2 @MIL-101). The catalyst shows full yield for the conversion of mesitylene to 2-iodomesitylene at a rate that is similar to the homogeneous POM system. Moreover, the catalyst is applicable for a wide range of substrates in an oxygen atmosphere without using any co-catalysts or sacrificial agents. To the best of our knowledge, this is the first report on designing a sustainable and green MOF-based heterogeneous catalytic system for the direct iodination reaction using molecular oxygen and iodine.