Abstract:Breaking point: An effective reductive cleavage of inert aryl CO bonds with an inexpensive iron catalyst has been developed. During this process, the reduction of the arene rings was not observed. This catalytic system also enabled the selective cleavage of the β‐O‐4 linkage of lignin model compounds under an atmosphere of hydrogen, thus offering an opportunity for the depolymerization of lignin.
“…A homogeneous Fe-based Fe(acac) 3 catalyst [84] was found to be highly effective for the hydrogenolysis of b-O-4 lignin model compounds in toluene in the presence of t-BuONa and H 2 . However, due to the use of t-BuONa, the reactants should be protected by an inert atmosphere.…”
Section: Monometallic Catalysts For Lignin Hydrogenolysismentioning
This review briefs the emerging strategies for the designing of catalysts and catalytic systems to upgrade waste biomass into value-added chemicals, with an emphasis on the efforts and advances in our group. The review covers the valorization of chitin and lignin materials, which are most abundant N-containing and the most abundant aromatic polymers, respectively. In the chitin part, we show case existing examples on chitin monomer and chitin transformation into renewable, N-containing chemicals. Oxidation, hydrolysis, dehydration reactions will be introduced. In lignin part we mainly introduce novel catalyst for lignin hydrogenolysis, in particular Ni based monometallic and bimetallic catalysts. The structure-activity correlations will be discussed in detail. We finally describe some of the undergoing works in the group and highlight a few potential directions worth investigation in the future.
“…A homogeneous Fe-based Fe(acac) 3 catalyst [84] was found to be highly effective for the hydrogenolysis of b-O-4 lignin model compounds in toluene in the presence of t-BuONa and H 2 . However, due to the use of t-BuONa, the reactants should be protected by an inert atmosphere.…”
Section: Monometallic Catalysts For Lignin Hydrogenolysismentioning
This review briefs the emerging strategies for the designing of catalysts and catalytic systems to upgrade waste biomass into value-added chemicals, with an emphasis on the efforts and advances in our group. The review covers the valorization of chitin and lignin materials, which are most abundant N-containing and the most abundant aromatic polymers, respectively. In the chitin part, we show case existing examples on chitin monomer and chitin transformation into renewable, N-containing chemicals. Oxidation, hydrolysis, dehydration reactions will be introduced. In lignin part we mainly introduce novel catalyst for lignin hydrogenolysis, in particular Ni based monometallic and bimetallic catalysts. The structure-activity correlations will be discussed in detail. We finally describe some of the undergoing works in the group and highlight a few potential directions worth investigation in the future.
“…In 2013, Wang reported a reductive cleavage of aryl ethers using catalytic amounts of Fe(acac) 3 (Scheme 27). 59 Undoubtedly, the recent developments in catalytic reductive cleavage have opened up new vistas in the field of C-O bondfunctionalization. 8, 47 The reasonably high temperatures required for effecting the targeted C-O bond-cleavage, however, invites the design of more powerful, yet practical, protocols that deal with such challenge.…”
In 1979, the seminal work of Wenkert set the standards for the utilization of aryl and vinyl ethers as coupling partners via C-O bond-cleavage. Although the topic remained dormant for almost three decades, the last years have witnessed a renaissance in this area of expertise, experiencing an exponential growth and becoming a significant discipline within the cross-coupling arena. The means to utilize readily accessible aryl or vinyl ethers as counterparts does not only represent a practical, powerful and straightforward alternative to organic halides, but also constitutes an excellent opportunity to improve our chemical knowledge on a relative unexplored area of expertise. This review summarizes the most significant developments in the area of C-O bond-cleavage when employing aryl or vinyl ethers, providing a detailed overview of the current state of the art and including future aspects, when applicable.
“…Preserving the aromatic rings while selectively cleaving the C–O bonds in phenols is a highly challenging task because the C–O bond in aryl ethers is strong, especially for that in phenol (414 kJ mol −1 ). There is therefore a well-known competition between the hydrogenolysis of C–O bonds and the hydrogenation of the aromatic rings during the lignin hydrodeoxygenation23242526. Unfortunately, the latter is thermodynamically favoured and, as a result, selective production of arenes from lignin upgrading is rarely reported27.…”
Lignin is the only large-volume renewable source of aromatic chemicals. Efficient depolymerization and deoxygenation of lignin while retaining the aromatic functionality are attractive but extremely challenging. Here we report the selective production of arenes via direct hydrodeoxygenation of organosolv lignin over a porous Ru/Nb2O5 catalyst that enabled the complete removal of the oxygen content from lignin. The conversion of birch lignin to monomer C7–C9 hydrocarbons is nearly quantitative based on its monomer content, with a total mass yield of 35.5 wt% and an exceptional arene selectivity of 71 wt%. Inelastic neutron scattering and DFT calculations confirm that the Nb2O5 support is catalytically unique compared with other traditional oxide supports, and the disassociation energy of Caromatic–OH bonds in phenolics is significantly reduced upon adsorption on Nb2O5, resulting in its distinct selectivity to arenes. This one-pot process provides a promising approach for improved lignin valorization with general applicability.
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