Iron porphyrins-catalysed oxidation of α-alkyl substituted mono and dimethoxylated benzyl alcohols

Fabbri, Claudia; Aurisicchio, Claudia; Lanzalunga, Osvaldo

doi:10.2478/s11532-008-0005-8

Cited by 16 publications

(16 citation statements)

References 34 publications

(37 reference statements)

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Based on the different structure of the lignin precursors, the oxidation reaction pathways can be divided into three categories. First, p-coumaryl alcohol resembling lignin model compounds to 4-hydrobenzaldehyde [18,26,41,43] and then 4-hydrobenzoic acid [106]; Second, coniferyl alcohol resembling lignin model compounds to vanillin [9,81] and vanillic acid [36]; Third, sinapyl alcohol resembling lignin model compounds to syringaldehyde and syringic acid.…”

Section: Lignin To Phenolic Acidsmentioning

confidence: 99%

Catalytic Conversion of Lignocellulosic Biomass to Value-Added Organic Acids in Aqueous Media

Lin

Liu

et al. 2014

Green Chemistry and Sustainable Technology

View full text Add to dashboard Cite

The transition from today's fossil-based economy to a sustainable economy based on renewable biomass is driven by the concern of climate change and anticipation of dwindling fossil resources. Although biofuels are the central theme of the transition, biomass resources cannot completely replace petroleum. It is projected that biofuels can only supply up to 30 % of today's transportation fuel market even if all available domestic biomass resources are used for the production of liquid fuels. Therefore, transformation of biomass into high-value-added chemicals is advantageous to secure optimal use of the abundant, but limited, biomass resources from the economical and ecological perspective. Industry is increasingly considering bio-based chemical production as an attractive area for investment. The potential for chemical and polymer production from biomass is substantial. The US Department of Energy recently issued a report which listed 12 chemical building blocks considered as potential building blocks for the future. Organic acids (e.g., succinic, lactic, levulinic acid, etc.) are among the widely spread ''platform-molecules,'' which may be further converted into possibly derivable high-value-added chemicals. The transition from a fossil chemical industry to a renewable chemical industry will likewise depend on our ability to focus research and development efforts on the most promising alternatives. In this chapter, we review the emerging technologies on catalytic conversion of biomass to value-added organic acids in aqueous media.

show abstract

Section: Lignin To Phenolic Acidsmentioning

confidence: 99%

Catalytic Conversion of Lignocellulosic Biomass to Value-Added Organic Acids in Aqueous Media

Lin

Liu

et al. 2014

Green Chemistry and Sustainable Technology

View full text Add to dashboard Cite

show abstract

“…[15,16] In conclusion, we have found that rhenium-based catalysts are very effective in the dehydration of benzylic alcohols. Re 2 O 7 (0.5 mol %) was shown to perform better in this reaction than the current benchmark catalyst, sulfuric acid (2.5 mol %).…”

mentioning

confidence: 99%

Catalytic Dehydration of Benzylic Alcohols to Styrenes by Rhenium Complexes

2010

View full text Add to dashboard Cite

The catalytic dehydration of (poly)alcohols represents a facile route to (functionalized) olefins. Current dehydration methods use strong acids, such as sulfuric acid or p-toluenesulfonic acid (pTSA), [1] or solid acids, such as zeolites [2] or metal oxides. [3,4] The major problems with these methods are their low selectivity and low functional group tolerance. Therefore a selective, widely useable dehydration method is highly desirable. Such a method might prove useful in the dehydration of biomassbased compounds, which are very rich in hydroxyl groups. Dehydration of both the (hemi)cellulosic components of biomass as well as aromatic lignin components could provide very interesting building blocks for the chemical industry. [5,6] To date only a few alcohol-to-olefin dehydration reactions catalyzed by homogeneous catalysts have been reported. Catalysts based on ruthenium [7,8] have proven active in the combined dehydration/hydrogenation of diols, and also palladium- [9] and zinc-based [10] catalysts have been reported for the dehydration of alcohols. A remarkable non-metal-based dehydration of glycerol and erythritol that makes use of formic acid was recently reported by Ellman et al. [11] High-valent rhenium complexes have also shown promising activity in dehydration reactions. Multiple methods were reported: Methyltrioxorhenium(VII) (MTO; CH 3 ReO 3 ) showed good results at room temperature in the dehydration of various alcohols, [12] while in the presence of hydrogen at higher temperature and pressure epoxides were deoxygenated in good and diols in moderate yield.[13] Cp*ReO 3 performed very well in the presence of PPh 3 in the deoxygenation of various diols and polyols, [14] however, phosphine oxide was obtained as a byproduct in quantitative amounts. Herein, we report on a study into various rhenium-based catalysts for the dehydration of alcohols to olefins under mild conditions. We initially focused on the dehydration of various benzylic alcohols.Following the original procedure by Zhu and Espenson, [12] the first attempts using MTO as a catalyst for the dehydration of 1,2,3,4-tetrahydronaphthol 1 to 1,2-dihydronaphthalene 2 (Scheme 1) at room temperature gave surprisingly poor results. The yield of 2 using benzene as a solvent was only 4 %, while 71 % was originally reported. In our hands, the highest yield of 2 obtained was 10 %, using THF as solvent, a reaction time of 3 days, and 10 mol % MTO as catalyst at room temperature. Using the same procedure at elevated temperature, however, gave very good results. In toluene at 100 8C, complete conversion was obtained after as little as 30 min reaction time, yielding olefin 2 as the single product. Lowering the amount of catalyst to 1 mol % also resulted in complete conversion after 30 min. Next, different commercially available rhenium complexes were tested for their activity in reaction 1. A blank reaction gave low conversion after 3 days of reaction time, yielding a mixture of both olefin and ether. Re 2 (CO) 10 did show some activity, yet poor selectivity...

show abstract

“…10 Fabbri et al reported the oxidation of a series of a-alkylsubstituted mono and dimethoxylated benzyl alcohols catalyzed by FeTMPyPCl and FeTSPPCl with selectivity up to 49% in aqueous solutions. 11 Wietzerbin reported the catalytic oxidation of tertiary alcohols in water-soluble Mn-TMPyP/KHSO 5 systems, but many products were obtained with poor selectivity. 12 Subsequently, as a part of our studies on metalloporphyrinscatalyzed oxidations, 13 a controllable oxidation procedure for alcohols for corresponding acids or aldehydes catalyzed by water-soluble metalloporphyrins (MnTEPyP), has been developed (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

Highly efficient controllable oxidation of alcohols to aldehydes and acids with sodium periodate catalyzed by water-soluble metalloporphyrins as biomimetic catalyst

Ren

Chen

Zhou

et al. 2010

Bioorganic & Medicinal Chemistry

View full text Add to dashboard Cite

Iron porphyrins-catalysed oxidation of α-alkyl substituted mono and dimethoxylated benzyl alcohols

Cited by 16 publications

References 34 publications

Catalytic Conversion of Lignocellulosic Biomass to Value-Added Organic Acids in Aqueous Media

Catalytic Conversion of Lignocellulosic Biomass to Value-Added Organic Acids in Aqueous Media

Catalytic Dehydration of Benzylic Alcohols to Styrenes by Rhenium Complexes

Highly efficient controllable oxidation of alcohols to aldehydes and acids with sodium periodate catalyzed by water-soluble metalloporphyrins as biomimetic catalyst

Contact Info

Product

Resources

About