One of the most widely employed strategies to produce chiral molecules involves the asymmetric hydrogenation of functionalized olefins using rhodium catalysts. Despite their excellent performance, the exact identity of the active Rh species is still ambiguous as each site may plausibly feature one or two phosphorus ligands. In this work, we used a sequential postsynthetic modification approach to successfully incorporate single-site Rh species into a zirconium-based metal−organic framework comprised of chiral spinol-based ligands. These Rh species feature one phosphorus ligand per Rh, which contrasts with the molecular analogue that contains two phosphorus ligands per Rh site. Following extensive characterization of the Rh-monophosphorus material using techniques including solid-state NMR and extended X-ray absorption fine-structure (EXAFS) spectroscopy, we studied their catalytic performance in the asymmetric hydrogenations of enamides and α-dehydroamino acid esters and observed excellent yields and enantioselectivities (up to 99.9% ee). Notably, the Rhmonophosphorus catalyst is 5 times more active than the homogeneous Rh-biphosphorus control, which we attributed to the higher activity of the single-site Rh-monophosphorus species and the confined MOF cavities that can enrich reactants. In addition, we observed a unique topology-dependent behavior in which linker expansion leads to the formation of a novel Zr-MOF with a distinct 4,8-connected net that cannot be phosphorylated, presumably due to intense tensile strain and steric repulsion present within this framework. Finally, we demonstrate the utility of this single-site Rh-monophosphorus catalyst in the gram-scale synthesis of (R)cinacalcet hydrochloride, a first-in-class drug in the therapy of secondary hyperparathyroidism and parathyroid carcinoma, with 99.1% ee.
The quest for new and unique polynuclear metal-oxocarboxylate clusters has led to a continual boom of highly connected and robust metal−organic frameworks (MOFs) with intriguing properties. In this work, by virtue of a highly specific coordination-driven cluster rearrangement process of a presynthesized trinuclear zirconocene-based tripodal metallo-pyridine ligand, we realized the preparation of the first two 2D heterometallic MOFs incorporating unprecedented Johnson-type (J 51 ) nonanuclear Zr-oxocarboxylate clusters, as unambiguously uncovered by single-crystal X-ray crystallography. The resultant two charged frameworks feature counteranion-dependent 3,6-c kgd (JMOF-1) and 3,12-c 3,12L4 (JMOF-2) nets that are formed by octahedral and hexagonal prismatic Zr 9 molecular building blocks (MBBs), respectively. In addition, JMOF-2 shows promise for the purification of acetylene from CO 2 and C 2 H 4 , with IAST selectivities of about 12 and 8, respectively, at 298 K and 1 bar, as well as remarkable iodine capture capacity of up to 2.4 g g −1 .
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