title: Breaking the Dogma of Aldolase Specificity: Simple Aliphatic Ketones and Aldehydes are Nucleophiles for Fructose-6-phosphate Aldolase.
abstract: d-Fructose-6-phosphate aldolase (FSA) was probed for extended nucleophile promiscuity by using a series of fluorogenic substrates to reveal retro-aldol activity. Four nucleophiles ethanal, propanone, butanone, and cyclopentanone were subsequently confirmed to be non-natural substrates in the synthesis direction using the wild-type enzyme and its D6H variant. This exceptional widening of the nucleophile substrate scope offers a rapid entry, in good yields and high stereoselectivity, to less oxygenated alkyl ketones and aldehydes, which was hitherto impossible.
authors.affiliation: Departamento de Química Biológica y Modelización Molecular, Instituto de Química Avanzada de Cataluña IQAC-CSIC, Jordi Girona 18-26, 08034, Barcelona, Spain.
authors.forename: Raquel
authors.initials: R
authors.lastname: Roldán
authors.affiliation: Université Clermont Auvergne, CNRS, SIGMA Clermont, Institut de Chimie de Clermont-Ferrand, 63000, Clermont-Ferrand, France.
authors.forename: Israel
authors.initials: I
authors.lastname: Sanchez-Moreno
authors.affiliation: Institut für Organische Chemie und Biochemie, Alarich-Weiss-Str. 4, 64287, Darmstadt, Germany.
authors.forename: Thomas
authors.initials: T
authors.lastname: Scheidt
authors.affiliation: Université Clermont Auvergne, CNRS, SIGMA Clermont, Institut de Chimie de Clermont-Ferrand, 63000, Clermont-Ferrand, France.
authors.forename: Virgil
authors.initials: V
authors.lastname: Hélaine
authors.affiliation: Université Clermont Auvergne, CNRS, SIGMA Clermont, Institut de Chimie de Clermont-Ferrand, 63000, Clermont-Ferrand, France.
authors.forename: Marielle
authors.initials: M
authors.lastname: Lemaire
authors.affiliation: Servei de Ressonancia Magnetica Nuclear, Universitat Autonoma de Barcelona, Bellaterra, Spain.
authors.forename: Teodor
authors.initials: T
authors.lastname: Parella
authors.affiliation: Departamento de Química Biológica y Modelización Molecular, Instituto de Química Avanzada de Cataluña IQAC-CSIC, Jordi Girona 18-26, 08034, Barcelona, Spain.
authors.forename: Pere
authors.identifier: http://orcid.org/0000-0001-5541-4794
authors.initials: P
authors.lastname: Clapés
authors.affiliation: Institut für Organische Chemie und Biochemie, Alarich-Weiss-Str. 4, 64287, Darmstadt, Germany.
authors.forename: Wolf-Dieter
authors.initials: WD
authors.lastname: Fessner
authors.affiliation: Université Clermont Auvergne, CNRS, SIGMA Clermont, Institut de Chimie de Clermont-Ferrand, 63000, Clermont-Ferrand, France.
authors.forename: Christine
authors.identifier: http://orcid.org/0000-0002-7115-9831
authors.initials: C
authors.lastname: Guérard-Hélaine
mesh_terms: D000446:Aldehyde-Lyases / Q000737:chemistry / Q000378:metabolism*; D000447:Aldehydes / Q000737:chemistry*; D002384:Catalysis; D005634:Fructose-Bisphosphate Aldolase / Q000737:chemistry / Q000378:metabolism*; D005636:Fructosephosphates / Q000737:chemistry*; D007659:Ketones / Q000737:chemistry*; D015394:Molecular Structure; D013237:Stereoisomerism
chemical_list: D000447:Aldehydes; D005636:Fructosephosphates; D007659:Ketones; C027618:fructose-6-phosphate; D000446:Aldehyde-Lyases; D005634:Fructose-Bisphosphate Aldolase
keywords: aldolization; biocatalysis; enzymes; fructose-6-phosphate aldolase; phosphorylated compounds