General and selective deoxygenation by hydrogen using a reusable earth-abundant metal catalyst

Schwob, Tobias; Kunnas, Peter; Jonge, Niels de; Papp, Christian; Kempe, Rhett

doi:10.1126/sciadv.aav3680

Cited by 43 publications

(34 citation statements)

References 42 publications

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“…The novel Ni/C catalyst was synthesized in a practical two‐step procedure according to the synthesis concept for 3d metal catalysts developed by us [10d–g] (Figure 1): Firstly, the commercially available carbon support (Norit CA1) was wet impregnated with the novel Ni‐salen(prop)(di‐ tert ‐butyl) complex in tetrahydrofuran and the solvent was removed (see Supporting Information for crystallographic data and complex characterization). This was followed by a pyrolysis step at 700 °C in nitrogen atmosphere and a reduction step at 550 °C in forming gas (90/10, N 2 /H 2 ).…”

Section: Resultsmentioning

confidence: 99%

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Chemoselective Hydrogenation of Olefins Using a Nanostructured Nickel Catalyst

Klarner

Bieger

Drechsler

et al. 2021

Zeitschrift anorg allge chemie

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The selective hydrogenation of functionalized olefins is of great importance in the chemical and pharmaceutical industry. Here, we report on a nanostructured nickel catalyst that enables the selective hydrogenation of purely aliphatic and functionalized olefins under mild conditions. The earth-abundant metal catalyst allows the selective hydrogenation of sterically pro-tected olefins and further tolerates functional groups such as carbonyls, esters, ethers and nitriles. The characterization of our catalyst revealed the formation of surface oxidized metallic nickel nanoparticles stabilized by a N-doped carbon layer on the active carbon support.

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Section: Resultsmentioning

confidence: 99%

“…The Ni/C catalyst is easy‐to‐synthesize in a two‐step procedure starting from inexpensive charcoal as support material. By controlled decomposition of a Ni‐salen complex precursor, catalytically active Ni nanoparticles are generated and at the same time stabilized in a nitrogen‐doped carbon matrix on the support [10d–g,11f] …”

Section: Introductionmentioning

confidence: 99%

Chemoselective Hydrogenation of Olefins Using a Nanostructured Nickel Catalyst

Klarner

Bieger

Drechsler

et al. 2021

Zeitschrift anorg allge chemie

Self Cite

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“…Therefore, the development of heterogeneous catalysts based on earth-abundant metals for hydrodeoxygenation under mild condition is challenging but highly attractive for economic reasons. Despite recent progress on supported earth-abundant metal nanoparticles-based catalysts for hydrodeoxygenation, − the requirement of high catalyst loading, high pressure of hydrogen, limited substrate scope, and ill-defined active sites limits their practical applicability and also complicates the investigation of the mechanism.…”

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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“…Therefore, direct and selective transformation of naturally abundant functional groups is very important to increase efficiency in organic synthesis ( Palacios et al., 2007 ; Veitch et al., 2007 ). In particular, the deoxygenation reaction provides an enabling tool for future biorefinery concepts through the cleavage of C-O bonds ( Ruppert et al., 2012 ; Li et al., 2020 ; Schwob et al., 2019 ; Volkov et al., 2015 ; Wang et al., 2018 ), which allows the conversion of biomass-based readily available alcohols and polyols into platform chemicals and fuels ( Bozell and Petersen, 2010 ; Corma et al., 2007 ; Dam and Hanefeld, 2011 ). The common methods for the deoxygenation of alcohols are divided into two categories: indirect and direct C–O bond cleavages.…”

Section: Introductionmentioning

confidence: 99%

Light-Driven Metal-Free Direct Deoxygenation of Alcohols under Mild Conditions

Cao

Chen

et al. 2020

iScience

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Summary Hydroxyl is widely found in organic molecules as functional group and its deprivation plays an inevitable role in organic synthesis. However, the direct cleavage of Csp 3 -O bond in alcohols with high selectivity and efficiency, especially without the assistance of metal catalyst, has been a formidable challenge because of its strong bond dissociation energy and unfavorable thermodynamics. Herein, an efficient metal-free strategy that enables direct deoxygenation of alcohols has been developed for the first time, with hydrazine as the reductant induced by light. This protocol features mild reaction conditions, excellent functional group tolerance, and abundant and easily available starting materials, rendering selective deoxygenation of a variety of 1° and 2° alcohols, vicinal diols, and β -1 and even β -O-4 models of natural wood lignin. This strategy is also highlighted by its “traceless” and non-toxic by-products N 2 and H 2 , as readily escapable gases. Mechanistic studies demonstrated dimethyl sulfide being a key intermediate in this transformation.

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General and selective deoxygenation by hydrogen using a reusable earth-abundant metal catalyst

Abstract: A Co-Ce catalyst permits the hydrodeoxygenation of alcohols, aldehydes, and ketones, tolerating numerous functional groups.

Cited by 43 publications

References 42 publications

Chemoselective Hydrogenation of Olefins Using a Nanostructured Nickel Catalyst

Chemoselective Hydrogenation of Olefins Using a Nanostructured Nickel Catalyst

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

Light-Driven Metal-Free Direct Deoxygenation of Alcohols under Mild Conditions

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