Synthetic and computational assessment of a chiral metal–organic framework catalyst for predictive asymmetric transformation

Canivet, J.; Bernoud, Elise; Bonnefoy, J.; Legrand, Alexandre; Todorova, Tanya K.; Quadrelli, Elsje Alessandra; Mellot‐Draznieks, Caroline

doi:10.1039/d0sc03364b

Cited by 25 publications

(23 citation statements)

References 41 publications

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“…To change the paradigm of molecular catalytic processes for fine chemical synthesis, we introduced recently the concept of solid porous macroligand for heterogenized molecular catalysis (Scheme ). Having molecularly defined active sites, porous macroligands have been found to drive the activity and the selectivity of heterogenized catalytic processes on a similar way as molecular ligands but with the advantage of the structuration in a three-dimensional framework , and the confinement within a porous nanospace. , …”

Section: Introductionmentioning

confidence: 99%

“…28 Having molecularly defined active sites, porous macroligands have been found to drive the activity and the selectivity of heterogenized catalytic processes on a similar way as molecular ligands 29 but with the advantage of the structuration in a three-dimensional framework 30,31 and the confinement within a porous nanospace. 32,33 Among organo-based porous materials offering functional derivatizable building blocks, porous organic polymers (POPs) are appealing platforms for the design of porous macroligands due to their chemical robustness arising from their covalent C−C bond network. Such a stable network appear to be wellsuited to the strong basic conditions used in the homogeneous Ni-catalyzed benzothiophene C−H arylation reaction.…”

Section: Introductionmentioning

confidence: 99%

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Heterogenization of a Molecular Ni Catalyst within a Porous Macroligand for the Direct C–H Arylation of Heteroarenes

et al. 2021

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Direct C-H functionalization catalyzed by a robust and recyclable heterogeneous catalyst is highly desirable for sustainable fine chemical synthesis. Bipyridine units covalently incorporated into the backbone of a porous organic polymer were used as a porous macroligand for the heterogenization of a molecular nickel catalyst. A controlled nickel loading within the porous macroligand is achieved and the nickel coordination to the bpy sites is assessed at the molecular level using IR and solid-state NMR spectroscopy. The heterogenized Ni-bpy catalyst was successfully applied to the direct and fully selective C2 arylation of benzothiophenes, thiophene and selenophene, as well as for the arylation of free NH-indole. Recyclability of the catalyst was achieved by employing hydride activators to reach a cumulative turnover number of more than 300 after seven cycles of catalysis, which corresponds to a total productivity of 12 grams of 2-phenylbenzothiophene, chosen as model target biaryl, per gram of catalyst.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Heterogenization of a Molecular Ni Catalyst within a Porous Macroligand for the Direct C–H Arylation of Heteroarenes

et al. 2021

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“…8 Moreover, the MOF extended crystalline network allows for combining crystallographic techniques with computational studies to elucidate catalytic site nature and molecular catalytic mechanisms at play inside the porosity. [9][10][11][12][13][14][15][16][17][18][19] In molecular catalysis, phosphines are widely used ligands whose both electronic and steric properties strongly influence the catalytic activity of the bound metal cation. 20 Phosphines have become essential to drive the catalytic activity and selectivity in applications ranging from fine chemistry with asymmetry and C-C coupling reactions, to petrochemistry with valorization of olefins using catalyzed oligomerization, hydroformylation, hydrogenation and metathesis.…”

Section: Introductionmentioning

confidence: 99%

Heterogenized Molecular Rhodium Phosphine Catalyst within Metal-Organic Framework for Ethylene Hydroformylation

Samanta

Solé‐Daura

Rajapaksha

et al. 2022

Preprint

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Molecularly-defined organometallic rhodium phosphine complexes were efficiently heterogenized within a MOF structure without affecting neither their molecular nature nor their catalytic behavior. Phosphine-functionalized MOF-808 served as solid ligand in a series of eight rhodium phosphine catalysts. These MOF-heterogenized molecular catalysts showed activity up to 2100 h-1 for ethylene hydroformylation towards pro-pionaldehyde as sole carbon-containing product. Combined experimental and computational methods applied to this unique MOF-based molecular system allowed unravelling structure and evolution of the Rh active species within the MOF under catalytic conditions, in line with molecular mechanisms at play during the hydroformylation reaction. The MOF-808 designed as a porous crystalline macroligand for well-defined molecular catalysts allows benefiting from molecular-scale understanding of interactions and mechanisms as well as from stabilization through site-isolation and recycling ability.

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“…Metal–organic frameworks (MOFs) are an emerging class of porous and tunable molecular material to develop heterogeneous and well-defined earth-abundant metal catalysts. − MOFs, built from metal-oxo cluster-based secondary building units (SBUs) or nodes and organic bridging linkers, provide thermally and chemically robust solid platforms to afford site-isolated catalytically active species. − Unlike the traditional oxide supports such as silica, alumina, or other metal oxides, MOFs offer a unique oxide support at SBUs to prepare single-site base-metal catalysts, benefitting from their reticular synthesis, tunable pores, and the highly disperse and uniform hydroxyl groups of its SBUs. − Moreover, MOF-supported single-site catalysts provide both the leverages offered by homogeneous catalysts such as homogeneity of the active sites, reproducibility, and selectivity and those provided by heterogeneous counterparts such as excellent robustness and easy recycling of the catalysts. ,− Herein, we report an aluminum hydroxide SBUs in a robust MOF (DUT-5)-supported single-site cobalt(II) hydride catalyst (DUT-5-CoH) for chemoselective deoxygenation of a range of aromatic and aliphatic ketones, aldehydes, and primary and secondary alcohols, including biomass-derived substrates under 1 bar of H 2 (Figure ).…”

Section: Introductionmentioning

confidence: 99%

Metal–Organic Framework-Confined Single-Site Base-Metal Catalyst for Chemoselective Hydrodeoxygenation of Carbonyls and Alcohols

et al. 2021

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Chemoselective deoxygenation of carbonyls and alcohols using hydrogen by heterogeneous base-metal catalysts is crucial for the sustainable production of fine chemicals and biofuels. We report an aluminum metal−organic framework (DUT-5) node support cobalt(II) hydride, which is a highly chemoselective and recyclable heterogeneous catalyst for deoxygenation of a range of aromatic and aliphatic ketones, aldehydes, and primary and secondary alcohols, including biomass-derived substrates under 1 bar H 2 . The single-site cobalt catalyst (DUT-5-CoH) was easily prepared by postsynthetic metalation of the secondary building units (SBUs) of DUT-5 with CoCl 2 followed by the reaction of NaEt 3 BH. X-ray photoelectron spectroscopy and X-ray absorption nearedge spectroscopy (XANES) indicated the presence of Co II and Al III centers in DUT-5-CoH and DUT-5-Co after catalysis. The coordination environment of the cobalt center of DUT-5-Co before and after catalysis was established by extended X-ray fine structure spectroscopy (EXAFS) and density functional theory. The kinetic and computational data suggest reversible carbonyl coordination to cobalt preceding the turnover-limiting step, which involves 1,2-insertion of the coordinated carbonyl into the cobalt−hydride bond. The unique coordination environment of the cobalt ion ligated by oxo-nodes within the porous framework and the rate independency on the pressure of H 2 allow the deoxygenation reactions chemoselectively under ambient hydrogen pressure.

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Synthetic and computational assessment of a chiral metal–organic framework catalyst for predictive asymmetric transformation

Abstract: Understanding and controlling molecular recognition mechanisms at a chiral solid interface has been addressed in metal–organic framework catalysts for the asymmetric transfer hydrogenation reaction.

Cited by 25 publications

References 41 publications

Heterogenization of a Molecular Ni Catalyst within a Porous Macroligand for the Direct C–H Arylation of Heteroarenes

Heterogenization of a Molecular Ni Catalyst within a Porous Macroligand for the Direct C–H Arylation of Heteroarenes

Heterogenized Molecular Rhodium Phosphine Catalyst within Metal-Organic Framework for Ethylene Hydroformylation

Metal–Organic Framework-Confined Single-Site Base-Metal Catalyst for Chemoselective Hydrodeoxygenation of Carbonyls and Alcohols

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