Robust, Chiral, and Porous BINAP-Based Metal–Organic Frameworks for Highly Enantioselective Cyclization Reactions

We report here the design of BINAP-based metal–organic frameworks and their postsynthetic metalation with Rh complexes to afford highly active and enantioselective single-site solid catalysts for the asymmetric cyclization reactions of 1,6-enynes. Robust, chiral, and porous Zr-MOFs of UiO topology, BINAP-MOF (<b>I</b>) or BINAP-dMOF (<b>II</b>), were prepared using purely BINAP-derived dicarboxylate linkers or by mixing BINAP-derived linkers with unfunctionalized dicarboxylate linkers, respectively. Upon metalation with Rh­(nbd)₂BF₄ and [Rh­(nbd)­Cl]₂/AgSbF₆, the MOF precatalysts <b>I</b>·Rh­(BF₄) and <b>I</b>·Rh­(SbF₆) efficiently catalyzed highly enantioselective (up to 99% ee) reductive cyclization and Alder-ene cycloisomerization of 1,6-enynes, respectively. <b>I</b>·Rh catalysts afforded cyclization products at comparable enantiomeric excesses (ee’s) and 4–7 times higher catalytic activity than the homogeneous controls, likely a result of catalytic site isolation in the MOF which prevents bimolecular catalyst deactivation pathways. However, <b>I</b>·Rh is inactive in the more sterically encumbered Pauson–Khand reactions between 1,6-enynes and carbon monoxide. In contrast, with a more open structure, Rh-functionalized BINAP-dMOF, <b>II</b>·Rh, effectively catalyzed Pauson–Khand cyclization reactions between 1,6-enynes and carbon monoxide at 10 times higher activity than the homogeneous control. <b>II</b>·Rh was readily recovered and used three times in Pauson–Khand cyclization reactions without deterioration of yields or ee’s. Our work has expanded the scope of MOF-catalyzed asymmetric reactions and showed that the mixed linker strategy can effectively enlarge the open space around the catalytic active site to accommodate highly sterically demanding polycyclic metallocycle transition states/intermediates in asymmetric intramolecular cyclization reactions

Robust, Chiral, and Porous BINAP-Based Metal–Organic Frameworks for Highly Enantioselective Cyclization Reactions

We report here the design of BINAP-based metal–organic frameworks and their postsynthetic metalation with Rh complexes to afford highly active and enantioselective single-site solid catalysts for the asymmetric cyclization reactions of 1,6-enynes. Robust, chiral, and porous Zr-MOFs of UiO topology, BINAP-MOF (<b>I</b>) or BINAP-dMOF (<b>II</b>), were prepared using purely BINAP-derived dicarboxylate linkers or by mixing BINAP-derived linkers with unfunctionalized dicarboxylate linkers, respectively. Upon metalation with Rh­(nbd)₂BF₄ and [Rh­(nbd)­Cl]₂/AgSbF₆, the MOF precatalysts <b>I</b>·Rh­(BF₄) and <b>I</b>·Rh­(SbF₆) efficiently catalyzed highly enantioselective (up to 99% ee) reductive cyclization and Alder-ene cycloisomerization of 1,6-enynes, respectively. <b>I</b>·Rh catalysts afforded cyclization products at comparable enantiomeric excesses (ee’s) and 4–7 times higher catalytic activity than the homogeneous controls, likely a result of catalytic site isolation in the MOF which prevents bimolecular catalyst deactivation pathways. However, <b>I</b>·Rh is inactive in the more sterically encumbered Pauson–Khand reactions between 1,6-enynes and carbon monoxide. In contrast, with a more open structure, Rh-functionalized BINAP-dMOF, <b>II</b>·Rh, effectively catalyzed Pauson–Khand cyclization reactions between 1,6-enynes and carbon monoxide at 10 times higher activity than the homogeneous control. <b>II</b>·Rh was readily recovered and used three times in Pauson–Khand cyclization reactions without deterioration of yields or ee’s. Our work has expanded the scope of MOF-catalyzed asymmetric reactions and showed that the mixed linker strategy can effectively enlarge the open space around the catalytic active site to accommodate highly sterically demanding polycyclic metallocycle transition states/intermediates in asymmetric intramolecular cyclization reactions

Computational Design Principles of Two-Center First-Row Transition Metal Oxide Oxygen Evolution Catalysts

Computational screens for oxygen evolution reaction (OER) catalysts based on Sabatier analysis have seen great success in recent years; however, the concept of using chemical descriptors to form a reaction coordinate has not been put under scrutiny for complex systems. In this paper, we examine critically the use of chemical descriptors as a method for conducting catalytic screens. Applying density functional theory calculations to a two-center metal oxide model system, we show that the Sabatier analysis is quite successful for predicting activities and capturing the chemical periodic trends expected for the first-row transition metal series, independent of the proposed mechanism. We then extend this analysis to heterodimer metallic systemsmetal oxide catalysts with two different catalytically active metal centersand find signs that the Sabatier analysis may not hold for these more complex systems. By performing a principal component analysis on the computed redox potentials, we show (1) that a single chemical descriptor inadequately describes heterodimer overpotentials and (2) mixed-metal overpotentials cannot be predicted using only pure-metal redox potentials. We believe that the analysis presented in this article shows a need to move beyond the simple chemical descriptor picture when studying more complex mixed metal oxide OER catalysts