Laccase‐mediated Oxidations of Propargylic Alcohols. Application in the Deracemization of 1‐arylprop‐2‐yn‐1‐ols in Combination with Alcohol Dehydrogenases

González‐Granda, Sergio; Méndez‐Sánchez, Daniel; Lavandera, Iván; Gotor‐Fernández, Vicente

doi:10.1002/cctc.201901543

Cited by 22 publications

(20 citation statements)

References 62 publications

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“…Finally, also the laccase-TEMPO system is worth mentioning here as the organocatalytic nature of the actual oxidation agent (2,2,6,6-Tetramethylpiperidin-1-yl)oxyl, TEMPO) also implies non-enantioselectivity and therefore is well-suited for the full oxidation of racemic alcohols (Scheme 22) [96,[164][165][166][167][168][169][170][171]. Especially activated benzylic, allylic, or propargylic alcohols are readily converted into the corresponding ketones.…”

Section: Complete Oxidation Of Racemic Secondary Alcoholsmentioning

confidence: 99%

Biocatalytic Oxidation of Alcohols

et al. 2020

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Enzymatic methods for the oxidation of alcohols are critically reviewed. Dehydrogenases and oxidases are the most prominent biocatalysts, enabling the selective oxidation of primary alcohols into aldehydes or acids. In the case of secondary alcohols, region and/or enantioselective oxidation is possible. In this contribution, we outline the current state-of-the-art and discuss current limitations and promising solutions.

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Section: Complete Oxidation Of Racemic Secondary Alcoholsmentioning

confidence: 99%

Biocatalytic Oxidation of Alcohols

et al. 2020

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“…Mild oxidation by Lac proved to be suitable for sensitive compounds such as 2-thiophenemethanol [ 66 ], propargyl alcohols [ 67 ], or secondary alcohols [ 68 ]. Thiophenemethanol (10 mM) was converted to 2-thiophenecarboxaldehyde by an immobilized Lac/TEMPO system on an analytical scale.…”

Section: Laccase-catalyzed Reactionsmentioning

confidence: 99%

“…Deracemization of racemic alcohols (50 mM) was performed in one pot on a semipreparative scale. Depending on the source of ADH, both enantiomers were obtained with largely excellent conversions at up to >99% enantiomeric excess ( Figure 13 ) [ 67 ].…”

Section: Laccase-catalyzed Reactionsmentioning

confidence: 99%

Laccases and Tyrosinases in Organic Synthesis

Martı́nková

Křístková

Křen

2022

IJMS

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Laccases (Lac) and tyrosinases (TYR) are mild oxidants with a great potential in research and industry. In this work, we review recent advances in their use in organic synthesis. We summarize recent examples of Lac-catalyzed oxidation, homocoupling and heterocoupling, and TYR-catalyzed ortho-hydroxylation of phenols. We highlight the combination of Lac and TYR with other enzymes or chemical catalysts. We also point out the biological and pharmaceutical potential of the products, such as dimers of piceid, lignols, isorhamnetin, rutin, caffeic acid, 4-hydroxychalcones, thiols, hybrid antibiotics, benzimidazoles, benzothiazoles, pyrimidine derivatives, hydroxytyrosols, alkylcatechols, halocatechols, or dihydrocaffeoyl esters, etc. These products include radical scavengers; antibacterial, antiviral, and antitumor compounds; and building blocks for bioactive compounds and drugs. We summarize the available enzyme sources and discuss the scalability of their use in organic synthesis. In conclusion, we assume that the intensive use of laccases and tyrosinases in organic synthesis will yield new bioactive compounds and, in the long-term, reduce the environmental impact of industrial organic chemistry.

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“…Propargylic ketones were obtained in quantitative conversions (87-99% yields), thus demonstrating the efficiency of LMS in comparison with traditional chemical oxidants, and their stereoselective reduction easily allowed the access to both (R) or (S) alcohol enantiomers depending on the aromatic pattern substitution (97-99% e.e.) (Scheme 5b) [74]. The synthesis of active pharmaceutical ingredients (APIs) is a fertile ground for the exploitation of multienzymatic synthetic methodologies.…”

Section: Laccase-mediator Systems: From Alcohols Bio-oxidation To Integrated Chemoenzymatic Systemsmentioning

confidence: 99%

“…Scheme 5. Applications of LMS in multienzymatic and cascade processes aimed at the preparation of enantioenriched amines (route (a)) or alcohols (route (b))[73,74].…”

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confidence: 99%

Biocatalysis with Laccases: An Updated Overview

et al. 2020

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Laccases are multicopper oxidases, which have been widely investigated in recent decades thanks to their ability to oxidize organic substrates to the corresponding radicals while producing water at the expense of molecular oxygen. Besides their successful (bio)technological applications, for example, in textile, petrochemical, and detoxifications/bioremediations industrial processes, their synthetic potentialities for the mild and green preparation or selective modification of fine chemicals are of outstanding value in biocatalyzed organic synthesis. Accordingly, this review is focused on reporting and rationalizing some of the most recent and interesting synthetic exploitations of laccases. Applications of the so-called laccase-mediator system (LMS) for alcohol oxidation are discussed with a focus on carbohydrate chemistry and natural products modification as well as on bio- and chemo-integrated processes. The laccase-catalyzed Csp2-H bonds activation via monoelectronic oxidation is also discussed by reporting examples of enzymatic C-C and C-O radical homo- and hetero-couplings, as well as of aromatic nucleophilic substitutions of hydroquinones or quinoids. Finally, the laccase-initiated domino/cascade synthesis of valuable aromatic (hetero)cycles, elegant strategies widely documented in the literature across more than three decades, is also presented.

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Laccase‐mediated Oxidations of Propargylic Alcohols. Application in the Deracemization of 1‐arylprop‐2‐yn‐1‐ols in Combination with Alcohol Dehydrogenases

Abstract: Dedicated to Professor Marko D. Mihovilovic on occasion of his 50 th birthday.

Cited by 22 publications

References 62 publications

Biocatalytic Oxidation of Alcohols

Biocatalytic Oxidation of Alcohols

Laccases and Tyrosinases in Organic Synthesis

Biocatalysis with Laccases: An Updated Overview

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