Ecofriendly syntheses of phenothiazones and related structures facilitated by laccase – A comparative study

doi:https://doi.org/10.1016/j.tetlet.2016.07.016

Title: Ecofriendly syntheses of phenothiazones and related structures facilitated by laccase – A comparative study

Abstract

The biocatalytic synthesis of phenothiazones and related compounds has been achieved in an aqueous system under mild conditions facilitated by laccase oxidation. It was found that by coupling 2-aminothiophenol directly with 1,4-quinones, the product yields could be significantly increased compared to generating the 1,4-quinones in situ from the corresponding hydroquinones via laccase oxidation. However, laccase still proved to be pivotal for achieving highest product yields by catalyzing the final oxidation step. Furthermore, a difference in reactivity of aromatic and aliphatic amines toward 1,4-naphthoquinone is observed. Furthermore, this study provides a sustainable approach to the synthesis of a biologically important class of compounds.

Authors:

Cannatelli, Mark D. ^[1]; Ragauskas, Arthur J. ^[2]

Georgia Inst. of Technology, Atlanta, GA (United States)
Georgia Inst. of Technology, Atlanta, GA (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)

Publication Date:: 2016-07-06

Research Org.:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Joint Institute for Biological Sciences (JIBS)

Sponsoring Org.:: USDOE Office of Science (SC)

OSTI Identifier:: 1327722

Grant/Contract Number:: AC05-00OR22725

Resource Type:: Journal Article: Accepted Manuscript

Journal Name:: Tetrahedron Letters

Additional Journal Information:: Journal Volume: 57; Journal Issue: 33; Journal ID: ISSN 0040-4039

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; biocatalysis; green chemistry; laccase; phenothiazones; thiol-amine

Citation Formats


                    Cannatelli, Mark D., and Ragauskas, Arthur J. Ecofriendly syntheses of phenothiazones and related structures facilitated by laccase – A comparative study.  United States: N. p., 2016. 
        Web.  doi:10.1016/j.tetlet.2016.07.016.

Copy to clipboard


                    Cannatelli, Mark D., & Ragauskas, Arthur J. Ecofriendly syntheses of phenothiazones and related structures facilitated by laccase – A comparative study.  United States.  https://doi.org/10.1016/j.tetlet.2016.07.016

Copy to clipboard


                    Cannatelli, Mark D., and Ragauskas, Arthur J. Wed .  
        "Ecofriendly syntheses of phenothiazones and related structures facilitated by laccase – A comparative study".  United States.  https://doi.org/10.1016/j.tetlet.2016.07.016.  https://www.osti.gov/servlets/purl/1327722.

Copy to clipboard


                    
@article{osti_1327722,

  title        = {Ecofriendly syntheses of phenothiazones and related structures facilitated by laccase – A comparative study},

  author       = {Cannatelli, Mark D. and Ragauskas, Arthur J.},

  abstractNote = {The biocatalytic synthesis of phenothiazones and related compounds has been achieved in an aqueous system under mild conditions facilitated by laccase oxidation. It was found that by coupling 2-aminothiophenol directly with 1,4-quinones, the product yields could be significantly increased compared to generating the 1,4-quinones in situ from the corresponding hydroquinones via laccase oxidation. However, laccase still proved to be pivotal for achieving highest product yields by catalyzing the final oxidation step. Furthermore, a difference in reactivity of aromatic and aliphatic amines toward 1,4-naphthoquinone is observed. Furthermore, this study provides a sustainable approach to the synthesis of a biologically important class of compounds.},

  doi          = {10.1016/j.tetlet.2016.07.016},

  url          = {https://www.osti.gov/biblio/1327722},
  journal      = {Tetrahedron Letters},

  issn         = {0040-4039},

  number       = 33,

  volume       = 57,

  place        = {United States},

  year         = {2016},

  month        = {7}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

https://doi.org/10.1016/j.tetlet.2016.07.016

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 1 work

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Works referencing / citing this record:

Dioxygen Activation by Laccases: Green Chemistry for Fine Chemical Synthesis
journal, May 2018

Romero-Guido, Cynthia; Baez, Antonino; Torres, Eduardo
Catalysts, Vol. 8, Issue 6
https://doi.org/10.3390/catal8060223

Similar records in OSTI.GOV collections:

Laccase-catalyzed synthesis of 2,3-ethylenedithio-1,4-quinones

Journal Article Cannatelli, Mark D. ; Ragauskas, Arthur J. - Journal of Molecular Catalysis B: Enzymatic

Laccases (benzenediol:oxygen oxidoreductase EC 1.10.3.2) are part of a family of multicopper oxidases. These environmentally friendly enzymes require O ₂ as their only co-substrate and produce H ₂O as their sole by-product. As a result, they have acquired increasing use in biotechnological applications, particularly in the field of organic synthesis. In the current study, laccases have been employed to successfully couple 1,2-ethanedithiol to various substituted hydroquinones to produce novel 2,3-ethylenedithio-1,4-quinones in good yields via an oxidation–addition–oxidation–addition–oxidation mechanism. The reactions proceeded in one-pot under mild conditions (room temperature, pH 5.0). This study further supports the use of laccases as green toolsmore »« less
Cited by 12
https://doi.org/10.1016/j.molcatb.2015.05.016

Full Text Available
DT-diaphorase-catalyzed two-electron reduction of various p-benzoquinone- and 1,4-naphthoquinone epoxides

Journal Article Brunmark, A ; Cadenas, E ; Segura-Aguilar, J ; ... - Free Radical Biology and Medicine; (USA)

The oxidation of various quinones by H{sub 2}O{sub 2} results in quinone epoxide formation. The yield of epoxidation is inversely related to the degree of methyl substitution of the quinone and seems not to be dependent on the redox potential of the quinones studied. The following order of H{sub 2}O{sub 2}-mediated epoxidation of quinones was found: p-benzoquinone greater than or equal to 1,4-naphthoquinone greater than 2-methyl-p-benzoquinone greater than 2,6-dimethyl-p-benzoquinone greater than or equal to 2-methyl-1,4-naphthoquinone greater than 2,3-dimethyl-1,4-naphthoquinone. DT-Diaphorase reduces several quinone epoxides at different rates. The rate of quinone epoxide reduction cannot be related to either the redox potentialmore »« less
https://doi.org/10.1016/0891-5849(88)90076-7
Exploiting the oxidizing capabilities of laccases exploiting the oxidizing capabilities of laccases for sustainable chemistry

Thesis/Dissertation Cannatelli, Mark D.

Part one of this dissertation research has focused on harnessing the ability of laccases to generate reactive para-quinones in situ from the corresponding hydroquinones, followed by reaction with a variety of nucleophiles to perform novel carbon-carbon, carbon-nitrogen, and carbon-sulfur bond forming reactions for the synthesis of new and existing compounds. In part two of this dissertation, the fundamental laccase-catalyzed coupling chemistry developed in part one was applied to functionalize the surface of kraft lignin.
https://doi.org/10.2172/1376617

Full Text Available
A broad spectrum catalytic system for removal of toxic organics from water by deep oxidation. 1998 annual progress report

Technical Report Sen, A

'Toxic organics and polymers pose a serious threat to the environment, especially when they are present in aquatic systems. The objective of the research is the design of practical procedures for the removal and/or recycling of such pollutants by oxidation. This report summarizes the work performed in the first one and half years of a three year project. The authors had earlier described a catalytic system for the deep oxidation of toxic organics, such as benzene, phenol and substituted phenols, aliphatic and aromatic halogenated compounds, organophosphorus, and organosulfur compounds [1]. In this system, metallic palladium was found to catalyze themore »« less
https://doi.org/10.2172/13720

Full Text Available
Mechanisms of induction of cancer-protective enzymes: a unifying proposal

Journal Article Prochaska, H J ; De Long, M J ; Talalay, P - Proc. Natl. Acad. Sci. U.S.A.; (United States)

Induction of detoxification enzymes is a major mechanism whereby a wide variety of chemical agents protect rodents against neoplastic, mutagenic, and other toxicities of carcinogens. The enzyme NAD(P)H:(quinone acceptor) oxidoreductase can protect against the toxicities of quinones and is a useful marker for protective enzyme induction. Quinone reductase can be induced in murine Hepa 1c1c7 hepatoma cells and 3T3 embryo fibroblasts by compounds that are chemoprotectors in vivo, including some phenolic antioxidants, azo dyes, aromatic diamines, and aminophenols. Structurally dissimilar catechols (1,2-diphenols) and hydroquinones (1,4-diphenols) induced quinone reductase in these systems, but resorcinol (1,3-diphenol) and its substituted analogues are inactive.more »« less
https://doi.org/10.1073/pnas.82.23.8232

Similar Records

Title: Ecofriendly syntheses of phenothiazones and related structures facilitated by laccase – A comparative study

Abstract

Citation Formats

Dioxygen Activation by Laccases: Green Chemistry for Fine Chemical Synthesis journal, May 2018

Dioxygen Activation by Laccases: Green Chemistry for Fine Chemical Synthesis
journal, May 2018