Selective oxidative cleavage of terminal olefins into aldehydes catalyzed by copper(<scp>ii</scp>) complex

Chun, Myung‐Suk; Meng, Xiang‐Gao; Liao, Xia; Xiao, Pei

doi:10.1039/c5ra14093e

Cited by 29 publications

(10 citation statements)

References 55 publications

(44 reference statements)

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“…Indeed, no conversion of the terminal alkene in the cardanol triene was observed. Hence, this photooxygenation may be applied as orthogonal method to oxidations that specifically convert terminal double bonds [30,31] . Then, the CNSL mixture was subjected to the standard flow photo‐oxygenation conditions with a residence time of 10 min (Figure 2, top).…”

Section: Resultsmentioning

confidence: 99%

“…Hence, this photooxygenation may be applied as orthogonal method to oxidations that specifically convert terminal double bonds. [ 30 , 31 ] Then, the CNSL mixture was subjected to the standard flow photo‐oxygenation conditions with a residence time of 10 min (Figure 2 , top). The evolution of the peroxy functions was determined by downstream reduction with PPh 3 and quantification of the amount of formed triphenylphosphine oxide, OPPh 3 .…”

Section: Resultsmentioning

confidence: 99%

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Light‐Driven Waste‐To‐Value Upcycling: Bio‐Based Polyols and Polyurethanes from the Photo‐Oxygenation of Cardanols

Stuhr

Bayer²,

Stark

et al. 2021

ChemSusChem

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The upcycling of waste biomass into valuable materials by resource‐efficient chemical transformations is a prime objective for sustainable chemistry. This approach is demonstrated in a straightforward light‐driven synthesis of polyols and polyurethane foams from the multi‐ton waste products of cashew nut processing. The photo‐oxygenation of cardanol from nutshell oil results in the formation of synthetically versatile hydroperoxides. The choice of the workup method (i. e., reduction, hydrogenation, epoxidation) enables access to a diverse range of alcohols with tunable alkene and OH functions. Condensation with isocyanates to give rigid polyurethane foams provides a resource‐efficient waste‐to‐value chain that benefits from the availability of cardanol and installation of OH groups from aerial O2.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Light‐Driven Waste‐To‐Value Upcycling: Bio‐Based Polyols and Polyurethanes from the Photo‐Oxygenation of Cardanols

Stuhr

Bayer²,

Stark

et al. 2021

ChemSusChem

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“…Heretofore, various metal- and non-metal-based methods such as the Lemieux–Johnson protocol (OsO 4 /NaIO 4 system), transition metals (Ru, Pd, Re, Fe, Au, Mn, Mo, W) in the presence of oxidizing reagents, m -chloroperoxybenzoic acid ( m -CPBA), pyridinium chlorochromate (PCC), N -hydroxyphthalimide (NHPI), 2,2-azobis(isobutyronitrile) (AIBN), and photochemical methods have been applied as the oxidative cleavage systems. However, despite tremendous attempts made in this field, these methods still have many disadvantages. − In other words, using toxic, expensive, nonrenewable metal resources, toxic organic solvents, large amounts of oxidants, harsh conditions, producing excessive byproducts, low selectivity, and the need for PTC along with limited substrates are the features of the current cleavage systems. − Very recently, selenium-containing compounds as a nonmetal catalyst are reported as active and sustainable catalysts for the oxidative reaction in the presence of green oxidants. In this regard, Yu and co-workers synthesized polyselenides from the reaction of dihalohydrocarbons with NaHSe as a homogeneous oxidative cracking catalyst of alkenes in the presence of excess amount of H 2 O 2 as an oxidant .…”

Section: Resultsmentioning

confidence: 99%

Amphiphilic Carbon Quantum Dots as a Bridge to a Pseudohomogeneous Catalyst for Selective Oxidative Cracking of Alkenes to Aldehydes: A Nonmetallic Oxidation System

Hadian-Dehkordi

Rezaei

Ramazani

et al. 2020

ACS Appl. Mater. Interfaces

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The oxidative cleavage of alkenes to the corresponding aldehydes using new amphiphilic carbon quantum dots (A-CQDs) as a pseudohomogeneous carbocatalyst is achieved for the first time through green and sustainable chemical processes. In this work, we successfully design a recyclable pseudohomogeneous catalyst based on A-CQDs, which is decorated with 1-aminopropyl-3-methyl-imidazolium chloride and stearic acid. The functionalization is conducted to introduce a hydrophilic/hydrophobic functionality on the surface of the catalyst to achieve high catalyst availability in polar and nonpolar media with the green goal of eliminating organic (co)solvents and additives. This amphiphilic carbocatalyst provides high mass transferability to the biphasic system, which is beneficial to promoting the oxidative cracking of a variety of olefins into corresponding aldehydes with a substrate/A-CQD ratio of 150. Around 87% of the substrates are converted to the related aldehydes using the carbocatalyst in the presence of H2O2, in pure water, without using a phase-transfer catalyst or any additives and organic solvents, which is comparable with the current metal-based cleavage systems. Surprisingly, A-CQDs exhibit high catalytic activity for the scission of electron-deficient CC bond of coumarin derivatives, accompanied by the cleavage of C–O bonds to produce the corresponding salicylaldehyde derivatives without overoxidation to acid. As a brief conclusion, A-CQDs exhibit high conversion efficiency without significant loss of activity even after six catalytic cycles. The conversion of alkenes into aldehydes is fast and high-throughput without overoxidation to acids and is accompanied by excellent solubility and stability in various solvents. Moreover, the product and the catalyst are recoverable from the reaction medium by simple extraction. So, this pseudohomogeneous carbocatalyst promises new horizons in imminent “catalytic age”. All in all, this paper provides a significant and novel advancement in carbocatalyst chemistry.

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“…Aromatic aldehydes, high-value aromatic compounds containing carbonyl groups, are widely used in the food, perfume, pharmaceuticals, and chemical industries. − Nowadays, the limited supply and high price of the extract of spiceberry and environmental pollution caused by chemical synthesis have made researchers considering to develop a green and economical method for the synthesis of aromatic aldehydes. ,, Phenylpropanoid acids, natural secondary metabolites, are often released from the biomass of lignin, such as sugar beet pectin, coffee pulp, tobacco plants, and polysaccharides of graminaceous plants. − Significantly, phenylpropanoid acids could provide excellent carbon skeletons for synthesizing a wider range of highly value-added aromatic compounds. , Researchers have confirmed that phenylpropanoid acids could be transformed into aromatic aldehydes in the past 10 years. , Ferulic acid (FA), caffeic acid (CA), 4-hydroxycinnamic acid (HA), and cinnamic acid (CIA), which belong to natural phenylpropanoid acids with phenyl propylene units, are excellent precursors for aromatic aldehyde biosynthesis. , In addition, aromatic aldehydes produced from natural phenylpropanoid acids by biosynthesis are considered as a “flavoring agent” by the US and European legislation (Flavoring Regulation (EC) No. 1334/2008) .…”

Section: Introductionmentioning

confidence: 99%

Engineering a Feruloyl–Coenzyme A Synthase for Bioconversion of Phenylpropanoid Acids into High-Value Aromatic Aldehydes

Chen

Jiang

Kang³

et al. 2022

J. Agric. Food Chem.

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Aromatic aldehydes find extensive applications in food, perfume, pharmaceutical, and chemical industries. However, a limited natural enzyme selectivity has become the bottleneck of bioconversion of aromatic aldehydes from natural phenylpropanoid acids. Here, based on the original structure of feruloyl–coenzyme A (CoA) synthetase (FCS) from Streptomyces sp. V-1, we engineered five substrate-binding domains to match specific phenylpropanoid acids. FcsCIAE407A/K483L, FcsMAE407R/I481R/K483R, FcsHAE407K/I481K/K483I, FcsCAE407R/I481R/K483T, and FcsFAE407R/I481K/K483R showed 9.96-, 10.58-, 4.25-, 6.49-, and 8.71-fold enhanced catalytic efficiency for degrading CoA thioesters of cinnamic acid, 4-methoxycinnamic acid, 4-hydroxycinnamic acid, caffeic acid, and ferulic acid, respectively. Molecular dynamics simulation illustrated that novel substrate-binding domains formed strong interaction forces with substrates’ methoxy/hydroxyl group and provided hydrophobic/alkaline catalytic surfaces. Five recombinant E. coli with FCS mutants were constructed with the maximum benzaldehyde, p-anisaldehyde, p-hydroxybenzaldehyde, protocatechualdehyde, and vanillin productivity of 6.2 ± 0.3, 5.1 ± 0.23, 4.1 ± 0.25, 7.1 ± 0.3, and 8.7 ± 0.2 mM/h, respectively. Hence, our study provided novel and efficient enzymes for the bioconversion of phenylpropanoid acids into aromatic aldehydes.

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Selective oxidative cleavage of terminal olefins into aldehydes catalyzed by copper(ii) complex

Cited by 29 publications

References 55 publications

Light‐Driven Waste‐To‐Value Upcycling: Bio‐Based Polyols and Polyurethanes from the Photo‐Oxygenation of Cardanols

Light‐Driven Waste‐To‐Value Upcycling: Bio‐Based Polyols and Polyurethanes from the Photo‐Oxygenation of Cardanols

Amphiphilic Carbon Quantum Dots as a Bridge to a Pseudohomogeneous Catalyst for Selective Oxidative Cracking of Alkenes to Aldehydes: A Nonmetallic Oxidation System

Engineering a Feruloyl–Coenzyme A Synthase for Bioconversion of Phenylpropanoid Acids into High-Value Aromatic Aldehydes

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