Electronic Effects of Nitro, Nitroso, Amino and Related Groups

Shorter, J.

doi:10.1002/9780470682531.pat0081

Cited by 3 publications

(3 citation statements)

References 175 publications

(159 reference statements)

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“…In biological environments, the polarity of nitro-groups generates unique binding interactions with protein receptors and other molecules which enables application of nitroaromatics as antibiotics, antiparasitics, and chemotherapeutics (Nepali et al, 2019;Strauss, 1979). Specifically, the strong π electron delocalizing properties of the nitro group within aromatic 3 systems can enhance intermolecular interactions including arene-arene and aryl hydrogen anion bonding interactions (Bryantsev and Hay, 2005;Lewis et al, 2012;Shorter, 2009). While proteins could also benefit from the installation of these properties at specific sites, none of the twenty standard amino acids exhibit similar levels of electron-withdrawing potential.…”

Section: Introductionmentioning

confidence: 99%

“…The copyright holder for this preprint this version posted September 29, 2021. ; https://doi.org/10.1101/2021.09.29.462267 doi: bioRxiv preprint systems can enhance intermolecular interactions including arene-arene and aryl hydrogen anion bonding interactions (Bryantsev and Hay, 2005;Lewis et al, 2012;Shorter, 2009). While proteins could also benefit from the installation of these properties at specific sites, none of the twenty standard amino acids exhibit similar levels of electron-withdrawing potential.…”

Section: Introductionmentioning

confidence: 99%

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De novo biosynthesis of para-nitro-L-phenylalanine in Escherichia coli

Butler

Sen

Lin

et al. 2021

Preprint

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Nitroaromatic functional groups can impart valuable properties to chemicals and to biological macromolecules including polypeptides. Para-nitro-L-phenylalanine (pN-Phe) is a nitroaromatic amino acid with uses including immune stimulation and fluorescence quenching. As the chemical synthesis of pN-Phe does not follow green chemistry principles and impedes provision of pN-Phe to engineered bacterial cells in some contexts, we sought to design a de novo biosynthetic pathway for pN-Phe in Escherichia coli. To generate the nitro chemical functional group, we identified natural diiron monooxygenases with measurable in vitro and in vivo activity on envisioned amine-containing precursors of para-amino-L-phenylalanine (pA-Phe) and para-aminophenylpyruvate. By expressing one of these N-oxygenase genes together with previously characterized genes for the biosynthesis of pA-Phe, we achieved the synthesis of pN-Phe from glucose. Through further optimization of the chassis, plasmid constructs, and media conditions, we were able to improve the selectivity of pN-Phe biosynthesis, resulting in a maximum titer of 819 μM in rich defined media under shake-flask conditions. These results provide a foundation for the biosynthesis of related nitroaromatic chemicals and for downstream biological applications that could utilize pN-Phe as a building block.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

De novo biosynthesis of para-nitro-L-phenylalanine in Escherichia coli

Butler

Sen

Lin

et al. 2021

Preprint

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“…12,13 Though limited in scope, both approaches illustrate that photoinduced nitroarenes are capable of anaerobic alcohol oxidation. [14][15][16] Based on our previous Scheme 1: Prior Methods and Hypothesized Work work on hydrocarbon oxidation using nitroarene photochemistry, [17][18][19] we hypothesized the possibility of harnessing multiple HAT events with nitroarenes to promote the anaerobic oxidation of heteroatom systems under visible-light irradiation. Herein, we illustrate that the photoexcited state of the nitroarene can trigger a double HAT event with C(sp 3 )-heteroatom systems to generate valuable ketone and imines, and a successive HAT and oxygen atom transfer (OAT) event at C(sp 2 )-heteroatom systems to furnish synthetically useful carboxylic acids and amides.…”

mentioning

confidence: 99%

Photoinduced Nitroarenes as Versatile Anaerobic Oxidants for Accessing Carbonyl and Imine Derivatives

Mitchell,

Hussain,

Bansode

et al. 2023

Preprint

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Herein, we report a protocol for the anaerobic oxidation of alcohols, amines, aldehydes, and imines promoted by photoexcited nitroarenes. Mechanistic studies support that photoexcited nitroarenes undergo double hydrogen atom transfer (HAT) steps with alcohols and amines to provide respective ketone and imine products. However, in the presence of aldehydes and imines, a successive HAT and oxygen atom transfer (OAT) event occurs to yield carboxylic acids and amides, respectively. This transformation is amenable to a continuous-flow photochemical setup, which led to significantly reduced reaction times.

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