Cobalt-Catalyzed Asymmetric Addition of Silylacetylenes to 1,1-Disubstituted Allenes

The asymmetric addition of silylacetylenes to 1,1-disubstituted allenes proceeded in the presence of a cobalt/chiral bisphosphine ligand to give the corresponding enynes with high enantioselectivity. The results of deuterium-labeling experiments indicated that a hydrogen atom at the chiral center is originated from the terminal alkyne, and they were in good agreement with the proposed catalytic cycle where enantioselectivity is determined by the reaction of the proposed π-allylcobalt intermediate with the terminal alkyne

Cobalt-Catalyzed Asymmetric 1,6-Addition of (Triisopropylsilyl)-acetylene to α,β,γ,δ-Unsaturated Carbonyl Compounds

Asymmetric addition of (triisopropylsilyl)­acetylene to α,β,γ,δ-unsaturated carbonyl compounds took place in the presence of a cobalt/Duphos catalyst to give the 1,6-addition products in high yields with high regio- and enantioselectivity

Formation of Carbocycles via a 1,4-Rh Shift Triggered by a Rhodium-Catalyzed Addition of Terminal Alkynes to 3,3-Diarylcyclopropenes

The catalytic addition of terminal alkynes to 3,3-diarylcyclopropenes in the presence of a Rh­(I)/binap complex proceeded to give the cycloaddition products in good yields, where a 1,4-Rh shift is involved as a key step

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

Metal–Organic Frameworks Stabilize Mono(phosphine)–Metal Complexes for Broad-Scope Catalytic Reactions

Mono­(phosphine)–M (M–PR₃; M = Rh and Ir) complexes selectively prepared by postsynthetic metalation of a porous triarylphosphine-based metal–organic framework (MOF) exhibited excellent activity in the hydrosilylation of ketones and alkenes, the hydrogenation of alkenes, and the C–H borylation of arenes. The recyclable and reusable MOF catalysts significantly outperformed their homogeneous counterparts, presumably via stabilizing M–PR₃ intermediates by preventing deleterious disproportionation reactions/ligand exchanges in the catalytic cycles

Cerium-Hydride Secondary Building Units in a Porous Metal–Organic Framework for Catalytic Hydroboration and Hydrophosphination

We report the stepwise, quantitative transformation of Ce^IV₆(μ₃-O)₄(μ₃-OH)₄­(OH)₆(OH₂)₆ nodes in a new Ce-BTC (BTC = trimesic acid) metal–organic framework (MOF) into the first Ce^III₆(μ₃-O)₄(μ₃-OLi)₄(H)₆(THF)₆Li₆ metal-hydride nodes that effectively catalyze hydroboration and hydrophosphination reactions. CeH-BTC displays low steric hindrance and electron density compared to homogeneous organolanthanide catalysts, which likely accounts for the unique 1,4-regioselectivity for the hydroboration of pyridine derivatives. MOF nodes can thus be directly transformed into novel single-site solid catalysts without homogeneous counterparts for sustainable chemical synthesis

Privileged Phosphine-Based Metal–Organic Frameworks for Broad-Scope Asymmetric Catalysis

A robust and porous Zr metal–organic framework (MOF) based on a BINAP-derived dicarb­oxyl­ate linker, BINAP-MOF, was synthesized and post-synthetically metalated with Ru and Rh complexes to afford highly enantio­selective catalysts for important organic transformations. The Rh-functionalized MOF is not only highly enantio­selective (up to >99% ee) but also 3 times as active as the homogeneous control. XAFS studies revealed that the Ru-functionalized MOF contains Ru-BINAP pre­catalysts with the same coordination environment as the homogeneous Ru complex. The post-synthetically metalated BINAP-MOFs provide a versatile family of single-site solid catalysts for catalyzing a broad scope of asymmetric organic transformations, including addition of aryl and alkyl groups to α,β-unsaturated ketones and hydrogenation of substituted alkene and carbonyl compounds