Laccase‐Mediator System for Alcohol Oxidation to Carbonyls or Carboxylic Acids: Toward a Sustainable Synthesis of Profens

Galletti, Paola; Pori, Matteo; Funiciello, Federica; Soldati, Roberto; Ballardini, Alberto; Giacomini, Daria

doi:10.1002/cssc.201402136

Cited by 35 publications

(42 citation statements)

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“…In a preliminary attempt para‐ methoxybenzylamine ( 1a , 0.5 mmol), chosen as a model substrate, did not react (Table 1, entry 1). The use of unbuffered water as reaction medium, which gave good results with alcohols,19 in this case failed maybe due to inactivation of Laccase Tv at the basic pH generated by amine dissolution in H 2 O 21. The use of acetate buffer at pH 4.5 then resulted in a successful reaction and 1a was quantitatively converted in the corresponding aldehyde 2a in 24 h (Table 1, entry 2).…”

Section: Resultsmentioning

confidence: 91%

“…The bio‐oxidation of amines was initially investigated starting from the reaction conditions optimized for alcohol oxidation, as we previously reported:19 Laccase Tv (Sigma–Aldrich, 5 mg, 50 units), 2,2,6,6‐tetramethylpiperidine 1‐oxyl (TEMPO; free radical) 20 mol% in water (6 mL) at room temperature with O 2 bubbled into the reaction vessel for 30 sec. In a preliminary attempt para‐ methoxybenzylamine ( 1a , 0.5 mmol), chosen as a model substrate, did not react (Table 1, entry 1).…”

Section: Resultsmentioning

confidence: 99%

“…Recently, we reported an application of LMS in the oxidation of some primary alcohols to the corresponding aldehydes and carboxylic acids. Moreover, we succeeded in a relevant application, developing the LMS‐oxidation of 2‐arylpropanols (profenols) to the corresponding 2‐arylpropionic acids (profens), in high yields and with a complete retention of configuration 19. Concerning the oxidation of amines only few applications of laccases were reported, mainly on anilines 20…”

Section: Introductionmentioning

confidence: 99%

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Selective Oxidation of Amines to Aldehydes or Imines using Laccase‐Mediated Bio‐Oxidation

et al. 2015

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An efficienta nd practical chemo-enzymatic aerobic oxidation in water of benzylamines to obtain aldehydes or imines is described. Laccase from Trametes versicolor was chosena sb iocatalyst, and TEMPO (radical 2,2,6,6-tetramethylpiperidine 1oxyl) as mediator. As tudy on the pH dependence of the aqueous medium allowed us to realise af ine tuning on product selectivity.U nder our optimized reactionc onditions,t he bio-oxidation of as eries of primary,s econdary andc yclic amines has been achieved.

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Section: Resultsmentioning

confidence: 91%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Selective Oxidation of Amines to Aldehydes or Imines using Laccase‐Mediated Bio‐Oxidation

et al. 2015

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“…Galletti et al. reported that free laccase with (2,2,6,6‐tetramethyl‐piperidin‐1‐yl)oxyl (TEMPO) as the mediator could make the aerobic oxidation of some primary alcohols to the corresponding carboxylic acids or aldehydes . Because water is the only by‐product formed, in principle, laccase is an ideal catalyst for sustainable chemical processes …”

Section: Figurementioning

confidence: 99%

“…TEMPO can be easily recovered from the reaction mixture by extraction with organic solvents . The laccase–TEMPO system is considered to be the combination of two green and efficient catalysts and enables green aerobic oxidation . So the magnetic laccase catalyst with TEMPO as the mediator is an eco‐efficient catalysis for the oxidation of HMF to FDCA.…”

Section: Figurementioning

confidence: 99%

Efficient Catalytic Oxidation of 5‐Hydroxymethylfurfural to 2,5‐Furandicarboxylic Acid by Magnetic Laccase Catalyst

et al. 2018

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2,5-Furandicarboxylic acid (FDCA) is a bio-based platform chemical for the production of polyethylene furanoate (PEF) and other valuable furanic chemicals. A magnetic laccase catalyst with (2,2,6,6-tetramethyl-piperidin-1-yl)oxyl (TEMPO) as the mediator has the remarkable capability of oxidizing 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA). Under optimal reaction conditions, a quantitative yield (90.2 %) of FDCA with complete HMF conversion was obtained after 96 h of reaction. More importantly, the magnetic laccase catalyst exhibited good recyclability and stability, maintaining 84.8 % of its original activity following six reuse cycles. This is the first report on the efficient catalytic oxidation of HMF to FDCA by using an immobilized enzyme catalyst.

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Solvent‐Promoted Oxidation of Aromatic Alcohols/Aldehydes to Carboxylic Acids by a Laccase‐TEMPO System: Efficient Access to 2,5‐Furandicarboxylic Acid and 5‐Methyl‐2‐Pyrazinecarboxylic Acid

Cheng

Zong

et al. 2021

Advanced Sustainable Systems

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challenging, because most of the aerobic alcohol oxidations stop at the aldehyde stage even with noble metals. [4] In addition, many methods suffer from such drawbacks as use of environmentally unfriendly catalysts (e.g., metals) and/ or solvents (e.g., aqueous alkaline solutions and chloroalkanes), harsh reaction conditions, and unsatisfactory selectivities. According to Tojo and Fernández, [1a] approximately 40% of the processes toward carboxylic acids were still performed through a two-step oxidation, with the isolation of the aldehyde intermediates; therefore, this technique for direct access to carboxylic acids is still immature.Nitroxyl radicals are versatile organocatalysts for catalytic oxidations, where they, alone or in combination with other catalysts (e.g., transition metals, NO x and laccase), are used in the presence of oxidants. [5] 2,2,6,6-Tetramethylpiperidinyl-1-oxy (TEMPO) and its derivatives, a type of stable nitroxyl radicals, have been widely used for the production of pharmaceuticals, fragrances and flavors, agrochemicals, and specialty chemicals. [6] To date, few studies on catalytic oxidation of primary alcohols to carboxylic acids by nitroxyl radicals have been reported, [7] although the routes to aldehydes have been well established. [8] In Anelli's oxidation, primary alcohols were oxidized to carboxylic acids by TEMPO and KBr in a biphasic CH 2 Cl 2 /water mixture in the presence of a phasetransfer catalyst (Scheme 1a), with chlorine bleach (NaOCl) as an oxidant. [9] Then a series of modified Anelli's protocols were developed by using alternative oxidants (e.g., NaClO 2 , and bis(acetoxy)iodobenzene (BAIB)). [10] Yakura et al. reported a TEMPO-iodobenzene hybrid catalyst for the synthesis of carboxylic acids in acetic acid in the presence of peracetic acid (Scheme 1b). [11] Stahl and co-workers presented a clean direct electrochemical method to oxidize primary alcohols and aldehydes to carboxylic acids in the presence of 4-acetamido-TEMPO (Scheme 1c). [12] Ma and co-workers found that a threecomponent catalyst (TEMPO, Fe(NO 3 ) 3 •9H 2 O and KCl) enabled room-temperature aerobic oxidation of primary alcohols to carboxylic acids in 1,2-dichloroethane (Scheme 1d), [13] in which Fe(NO 3 ) 3 •9H 2 O catalyzed further oxidation of aldehydes to carboxylic acids. [14] From the perspective of green and sustainable Laccase coupled with 2,2,6,6-tetramethylpiperidinyl-1-oxy (TEMPO) is a wellknown catalytic system for the oxidation of alcohols to the carbonyl compounds. In this work, a simple yet effective solvent engineering strategy is developed to enable aromatic alcohols/aldehydes to be efficiently oxidized to carboxylic acids by a laccase-TEMPO system. Citrate buffer (100-300 mm, pH 6) rather than the widely used acetate buffer (pH 4-5) proves to be optimal for this purpose. The roles of citrate are discussed in laccase-TEMPOcatalyzed synthesis of carboxylic acids. 5-Hydroxymethylfurfural (HMF) of 200 mm is oxidized to 2,5-furandicarboxylic acid (FDCA), a top-value biobased chemical in the...

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Laccase‐Mediator System for Alcohol Oxidation to Carbonyls or Carboxylic Acids: Toward a Sustainable Synthesis of Profens

Cited by 35 publications

References 58 publications

Selective Oxidation of Amines to Aldehydes or Imines using Laccase‐Mediated Bio‐Oxidation

Selective Oxidation of Amines to Aldehydes or Imines using Laccase‐Mediated Bio‐Oxidation

Efficient Catalytic Oxidation of 5‐Hydroxymethylfurfural to 2,5‐Furandicarboxylic Acid by Magnetic Laccase Catalyst

Solvent‐Promoted Oxidation of Aromatic Alcohols/Aldehydes to Carboxylic Acids by a Laccase‐TEMPO System: Efficient Access to 2,5‐Furandicarboxylic Acid and 5‐Methyl‐2‐Pyrazinecarboxylic Acid

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