On the stereochemistry of the Baker's Yeast-mediated reduction of regioisomeric unsaturated aldehydes: Examples of enantioselectivity switch promoted by substrate-engineering

Brenna, Elisabetta; Fronza, Giovanni; Fuganti, Claudio; Gatti, Francesco G.; Manfredi, Alessia; Parmeggiani, Fabio; Ronchi, Paolo

doi:10.1016/j.molcatb.2012.02.003

Cited by 16 publications

(4 citation statements)

References 36 publications

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“…Among the first reported examples are the diesters of isomeric citraconic, mesaconic and itaconic acids [47] and the regioisomeric pair α‐methylcinnamaldehyde and 2‐benzylacrylaldehyde. [23] More recently, this method has been exploited very successfully for the synthesis of both enantiomers of a family of substituted β‐ketoesters, further manipulated to yield all possible stereoisomers of a number of lactone fragrances[ 15 , 16 , 17 ] as well as in the direct reduction of regioisomeric unsaturated lactones. [41] …”

Section: Introductionmentioning

confidence: 99%

“A Study in Yellow”: Investigations in the Stereoselectivity of Ene‐Reductases

et al. 2021

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Ene-reductases from the Old Yellow Enzyme (OYE) superfamily are a well-known and efficient biocatalytic alternative for the asymmetric reduction of C=C bonds. Considering the broad variety of substituents that can be tolerated, and the excellent stereoselectivities achieved, it is apparent why these enzymes are so appealing for preparative and industrial applications. Different classes of C=C bonds activated by at least one electron-withdrawing group have been shown to be accepted by these versatile biocatalysts in the last decades, affording a vast range of chiral intermediates employed in the synthesis of pharmaceuticals, agrochemicals, flavours, fragrances and fine chemicals. In order to access both enantiomers of reduced products, stereodivergent pairs of OYEs are desirable, but their natural occurrence is limited. The detailed knowledge of the stereochemical course of the reaction can uncover alternative strategies to orient the selectivity via mutagenesis, evolution, and substrate engineering. An overview of the ongoing studies on OYE-mediated bioreductions will be provided, with particular focus on stereochemical investigations by deuterium labelling.

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Section: Introductionmentioning

confidence: 99%

“A Study in Yellow”: Investigations in the Stereoselectivity of Ene‐Reductases

et al. 2021

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“…Peak integration reveals quantitative kinetic data . We follow the reaction mechanism by marking a nucleus with one of its isotopes and analyzing how it migrates with time . A common procedure to keep the magnetic field stable is to use an internal standard: in liquid‐state NMR is the 2 H signal from the deuterated solvent.…”

Section: Applicationsmentioning

confidence: 99%

Experimental Methods in Chemical Engineering: Nuclear Magnetic Resonance

2019

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Nuclear magnetic resonance (NMR) spectroscopy measures free induction decay (FID) signals that atomic nuclei emit when excited by a radiofrequency (RF) pulse in a static magnetic field. The Fourier-transformed spectrum shows chemically shifted peaks, area intensity, and multiplicity, which give information on molecular structure, bonds, functional groups, and purity. Web of Science Core Collection indexed 46 000 articles that mentioned NMR in 2016 and 2017. The VosViewer software grouped the research into 5 clusters: solid-state analysis including metabolomics; biology with in-vitro and antibacterial applications; coupled analytical techniques to identify crystal structure for which x-ray diffraction and density functional theory figure prominently; liquid-state analysis for polymers, aqueous solutions, nano-particles, and drug delivery; and chemosensors. Researchers publishing in The Canadian Journal of Chemical Engineering focus most on: liquid-state NMR to characterize polymers, branching, and monomers; quantify conformation, reaction kinetics, and equilibrium; and assess surfactant stability, ionic liquids, and composition. We introduce the theory behind NMR spectroscopy and common applications in chemistry and material science. We highlight the strength and limitations, sources of error, and the detection limit for this analytical technique, as manufacturers develop massive magnets for high-resolution spectra (1 GHz), and benchtop NMR for real-time, in-situ analysis (80 MHz).

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“… The correct choice of substrate structure can modify the outcome of the enzymatic transformation by influencing the binding mode of the substrate into the active site. [95,[108][109][110] For instance, altering the position of the double bond of unsaturated aldehydes can cause a switch in the enantioselectivity of enereductases. [109][110][111] The effect of protecting groups on the selectivity of the desymmetrization reaction of hydroxyaziridines catalysed by pig pancreatic lipase (PPL) was also described.…”

Section: Substrate Engineering In Enzymatic Transformationsmentioning

confidence: 99%

“…[95,[108][109][110] For instance, altering the position of the double bond of unsaturated aldehydes can cause a switch in the enantioselectivity of enereductases. [109][110][111] The effect of protecting groups on the selectivity of the desymmetrization reaction of hydroxyaziridines catalysed by pig pancreatic lipase (PPL) was also described. [112] CAL-B enantiopreference toward the production of carboxylic acids in view of the location of the stereocenter have been reviewed by Tsai.…”

Section: Substrate Engineering In Enzymatic Transformationsmentioning

confidence: 99%

Kinetic and dynamic kinetic enzymatic resolutions of tetrahydro-ß-carboline and tetrahydroisoquinoline derivatives

Megyesi¹

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On the stereochemistry of the Baker's Yeast-mediated reduction of regioisomeric unsaturated aldehydes: Examples of enantioselectivity switch promoted by substrate-engineering

Cited by 16 publications

References 36 publications

“A Study in Yellow”: Investigations in the Stereoselectivity of Ene‐Reductases

“A Study in Yellow”: Investigations in the Stereoselectivity of Ene‐Reductases

Experimental Methods in Chemical Engineering: Nuclear Magnetic Resonance

Kinetic and dynamic kinetic enzymatic resolutions of tetrahydro-ß-carboline and tetrahydroisoquinoline derivatives

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