Highly efficient Meerwein–Ponndorf–Verley reductions over a robust zirconium-organoboronic acid hybrid

Song, Jinliang; Hua, Manli; Huang, Xin; Visa, Aurelia; Wu, Tianbin; Fan, Honglei; Hou, Meiying; Zhang, Zhaofu; Han, Buxing

doi:10.1039/d0gc04179c

Cited by 44 publications

(34 citation statements)

References 42 publications

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“…Using LA as a substrate, a new type of organic zirconium borate (Zr-BDB) was developed by Song et al to convert it to GVL (Song et al, 2021). 1,4-Benzodiboric acid (BDB) and ZrOCl 2 .8H 2 O were synthesized by a solvothermal method in DMF (entry 1 of Table 5).…”

Section: La and Its Esters As Substratesmentioning

confidence: 99%

Recyclable Zr/Hf-Containing Acid-Base Bifunctional Catalysts for Hydrogen Transfer Upgrading of Biofuranics: A Review

Liu

et al. 2021

Front. Chem.

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The massive burning of a large amount of fossil energy has caused a lot of serious environmental issues (e.g., air pollution and climate change), urging people to efficiently explore and valorize sustainable alternatives. Biomass is being deemed as the only organic carbon-containing renewable resource for the production of net-zero carbon emission fuels and fine chemicals. Regarding this, the selective transformation of high-oxygen biomass feedstocks by catalytic transfer hydrogenation (CTH) is a very promising strategy to realize the carbon cycle. Among them, the important Meerwein-Ponndorf-Verley (MPV) reaction is believed to be capable of replacing the traditional hydrogenation strategy which generally requires high-pressure H2 and precious metals, aiming to upgrade biomass into downstream biochemical products and fuels. Employing bifunctional heterogeneous catalysts with both acidic and basic sites is needed to catalyze the MPV reaction, which is the key point for domino/cascade reaction in one pot that can eliminate the relevant complicated separation/purification step. Zirconium (Zr) and hafnium (Hf), belonging to transition metals, rich in reserves, can demonstrate similar catalytic efficiency for MPV reaction as that of precious metals. This review introduced the application of recyclable heterogeneous non-noble Zr/Hf-containing catalysts with acid-base bifunctionality for CTH reaction using the safe liquid hydrogen donor. The corresponding catalysts were classified into different types including Zr/Hf-containing metal oxides, supported materials, zeolites, metal-organic frameworks, metal-organic hybrids, and their respective pros and cons were compared and discussed comprehensively. Emphasis was placed on evaluating the bifunctionality of catalytic material and the key role of the active site corresponding to the structure of the catalyst in the MPV reaction. Finally, a concise summary and prospect were also provided centering on the development and suggestion of Zr/Hf-containing acid-base bifunctional catalysts for CTH.

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Section: La and Its Esters As Substratesmentioning

confidence: 99%

Recyclable Zr/Hf-Containing Acid-Base Bifunctional Catalysts for Hydrogen Transfer Upgrading of Biofuranics: A Review

Liu

et al. 2021

Front. Chem.

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“…The results clearly showed that the binding energy values of Zr 3d in Zr-AIER were much higher than those of ZrO 2 , indicating a higher positive charge on the Zr atoms in Zr-AIER, which leads to a stronger Lewis acidity. 21,26 We also examined the acidity and basicity of Zr-AIER and ZrO 2 by CO 2 -TPD and NH 3 -TPD methods (Fig. 2b and c), and the results suggested that Zr-AIER had higher acidity and basicity than ZrO 2 .…”

mentioning

confidence: 98%

“…Hydroxyl and carbonyl group activation is important for the high reactivity of MPV reduction. 21 It was reported that sulfonic acid/sulfonate could be used for the activation of hydroxyl and carbonyl groups, and thus the sulfonic acid group has the potential to be used in MPV reduction. 22 However, the sulfonic group in MPV reduction was just employed as the Brønsted acid to activate the substrate.…”

mentioning

confidence: 99%

“…Because of the higher reduction potential of primary alcohols, the yield of GVL in primary alcohols (Table S4, ESI† entries 1 and 2) was much lower than that in secondary alcohols (Table S4, ESI† entries 3 and 4). 21,26 b A significant decrease in the GVL yield was observed when using tert -butanol as the hydrogen donor (Table S4, ESI† entry 5); the reason could be attributed to the structure of tert -butanol, which leads to the difficulty of the hydrogen-transfer step in MPV reduction. 27…”

mentioning

confidence: 99%

“…Although great achievements have been made, the high cost of noble metals greatly limits future applications on a large scale, which makes the non-noble metal catalysts good candidates for the MPV reaction. Among the non-noble metal catalysts, Zr-based heterogeneous catalysts are the most widely used, and various organic ligands, including carboxylic acid, 19 phenol, 20 phosphoric acid, 16 and boric acid, 21 have been developed to promote their catalytic performance. However, there are still some drawbacks for Zr-based catalysts, such as complex preparation process, high cost of organic ligands, and harsh reaction conditions.…”

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confidence: 99%

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Amberlyst-15 supported zirconium sulfonate as an efficient catalyst for Meerwein–Ponndorf–Verley reductions

Wang¹,

Xie²,

Li³

et al. 2022

Chem. Commun.

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Effective one‐pot tandem synthesis of γ‐valerolactone from biogenic furfural over zirconium phosphate catalyst

Li²,

et al. 2022

Biofuels Bioprod Bioref

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γ-Valerolactone (GVL) is a renowned starting material in production of bio-fuels, valuable chemicals and polymers. The one-pot tandem synthesis of GVL from furfural without a cumbersome intermediate separation/purification process is highly desired, yet the transformation remains challenging owing to the complicated reaction routes. Zirconium phosphate (ZrPO), a cheap and easily prepared solid catalyst with Lewis-Brønsted dual acidity, is herein discovered to enable one-pot tandem transformation of furfural into GVL with using 2-propanol as H-donor/solvent to proceed smoothly. In addition, ZrPO prepared by hydrothermal method exhibits superior catalytic performance in comparison with the counterpart prepared by co-precipitation method, giving a 42.7% yield of GVL at 180 °C. The difference in catalytic activity between ZrPO materials prepared by hydrothermal method and co-precipitation method is linked with their morphology and acid sites density. Furthermore, the as-prepared ZrPO catalyst works in a heterogeneous manner and can be reused for multiple times without significant deactivation.

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Highly efficient Meerwein–Ponndorf–Verley reductions over a robust zirconium-organoboronic acid hybrid

Abstract: Synergetic effect of Zr4+ and borate in zirconium organoborate could significantly promote the Meerwein–Ponndorf–Verley reduction of various biomass-based carbonyl compounds.

Cited by 44 publications

References 42 publications

Recyclable Zr/Hf-Containing Acid-Base Bifunctional Catalysts for Hydrogen Transfer Upgrading of Biofuranics: A Review

Recyclable Zr/Hf-Containing Acid-Base Bifunctional Catalysts for Hydrogen Transfer Upgrading of Biofuranics: A Review

Amberlyst-15 supported zirconium sulfonate as an efficient catalyst for Meerwein–Ponndorf–Verley reductions

Effective one‐pot tandem synthesis of γ‐valerolactone from biogenic furfural over zirconium phosphate catalyst

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