Kuntal Manna, Pengfei Ji (co-first), Francis X. Greene, and Wenbin Lin*
Here we present the first example of a single-site main group catalyst stabilized by a metal–organic framework (MOF) for organic transformations. The straightforward metalation of the secondary building units of a Zr-MOF with Me2Mg affords a highly active and reusable solid catalyst for hydroboration of carbonyls and imines and for hydroamination of aminopentenes. Impressively, the Mg-functionalized MOF displayed very high turnover numbers of up to 8.4 × 104 for ketone hydroboration and could be reused more than 10 times. MOFs can thus be used to develop novel main group solid catalysts for sustainable chemical synthesis.