Catalytic Meerwein–Ponndorf–Verley reductions of ketones and aldehydes in the presence of isopropyl alcohol were performed at aluminum alkoxide sites that were postsynthetically introduced into robust metal–organic frameworks (MOFs). The aluminum was anchored at the bridging hydroxyl sites inherent in some MOFs. MOFs in the UiO-66/67 family as well as DUT-5 were successfully adapted to this strategy. Incorporation of catalytically active aluminum species greatly enhanced the reactivity of the native MOF at 80 °C in the case of both UiO-66, and was almost solely responsible for catalytic activity in the case of metalated UiO-66 and DUT-5. The site isolation of the catalyst prevented aggregation and complete deactivation of the molecular aluminum catalyst, allowing it to be recovered and recycled in the case of UiO-67. This catalyst also proved to be moderately tolerant to wet isopropyl alcohol.
Larson, P., Cheney, J. L., French, A. D., Klein, D., & Cozzolino, A. (2018). Anchored Aluminum Catalyzed Meerwein–Ponndorf–Verley Reduction at the Metal Nodes of Robust MOFs. Inorganic Chemistry, 6825-6832. https://doi.org/10.1021/acs.inorgchem.8b00119