Synthesis of Branched-Chain Sugars with a DHAP-Dependent Aldolase: Ketones are Electrophile Substrates of Rhamnulose-1-phosphate Aldolases
Victor Laurent
Université Clermont Auvergne, CNRS, SIGMA Clermont, Institut de Chimie de Clermont-Ferrand, 63000 Clermont-Ferrand, France
Search for more papers by this authorDr. Ekaterina Darii
Génomique Métabolique, Genoscope, Institut François Jacob, CEA, CNRS, Univ Evry, Univ Paris-Saclay, 91057 Evry, France
Search for more papers by this authorAngelina Aujon
Université Clermont Auvergne, CNRS, SIGMA Clermont, Institut de Chimie de Clermont-Ferrand, 63000 Clermont-Ferrand, France
Search for more papers by this authorMarine Debacker
Université Clermont Auvergne, CNRS, SIGMA Clermont, Institut de Chimie de Clermont-Ferrand, 63000 Clermont-Ferrand, France
Search for more papers by this authorJean-Louis Petit
Génomique Métabolique, Genoscope, Institut François Jacob, CEA, CNRS, Univ Evry, Univ Paris-Saclay, 91057 Evry, France
Search for more papers by this authorDr. Virgil Hélaine
Université Clermont Auvergne, CNRS, SIGMA Clermont, Institut de Chimie de Clermont-Ferrand, 63000 Clermont-Ferrand, France
Search for more papers by this authorDr. Tibor Liptaj
Slovak University of Technology, Faculty of Chemical and Food Technology, Radlinského 9, 81237 Bratislava, Slovakia
Search for more papers by this authorMartin Breza
Slovak University of Technology, Faculty of Chemical and Food Technology, Radlinského 9, 81237 Bratislava, Slovakia
Search for more papers by this authorAline Mariage
Génomique Métabolique, Genoscope, Institut François Jacob, CEA, CNRS, Univ Evry, Univ Paris-Saclay, 91057 Evry, France
Search for more papers by this authorLionel Nauton
Université Clermont Auvergne, CNRS, SIGMA Clermont, Institut de Chimie de Clermont-Ferrand, 63000 Clermont-Ferrand, France
Search for more papers by this authorDr. Mounir Traïkia
Université Clermont Auvergne, CNRS, SIGMA Clermont, Institut de Chimie de Clermont-Ferrand, 63000 Clermont-Ferrand, France
Search for more papers by this authorDr. Marcel Salanoubat
Génomique Métabolique, Genoscope, Institut François Jacob, CEA, CNRS, Univ Evry, Univ Paris-Saclay, 91057 Evry, France
These authors contributed equally to this work.
Search for more papers by this authorProf. Dr. Marielle Lemaire
Université Clermont Auvergne, CNRS, SIGMA Clermont, Institut de Chimie de Clermont-Ferrand, 63000 Clermont-Ferrand, France
These authors contributed equally to this work.
Search for more papers by this authorCorresponding Author
Dr. Christine Guérard-Hélaine
Université Clermont Auvergne, CNRS, SIGMA Clermont, Institut de Chimie de Clermont-Ferrand, 63000 Clermont-Ferrand, France
These authors contributed equally to this work.
Search for more papers by this authorCorresponding Author
Dr. Véronique de Berardinis
Génomique Métabolique, Genoscope, Institut François Jacob, CEA, CNRS, Univ Evry, Univ Paris-Saclay, 91057 Evry, France
These authors contributed equally to this work.
Search for more papers by this authorVictor Laurent
Université Clermont Auvergne, CNRS, SIGMA Clermont, Institut de Chimie de Clermont-Ferrand, 63000 Clermont-Ferrand, France
Search for more papers by this authorDr. Ekaterina Darii
Génomique Métabolique, Genoscope, Institut François Jacob, CEA, CNRS, Univ Evry, Univ Paris-Saclay, 91057 Evry, France
Search for more papers by this authorAngelina Aujon
Université Clermont Auvergne, CNRS, SIGMA Clermont, Institut de Chimie de Clermont-Ferrand, 63000 Clermont-Ferrand, France
Search for more papers by this authorMarine Debacker
Université Clermont Auvergne, CNRS, SIGMA Clermont, Institut de Chimie de Clermont-Ferrand, 63000 Clermont-Ferrand, France
Search for more papers by this authorJean-Louis Petit
Génomique Métabolique, Genoscope, Institut François Jacob, CEA, CNRS, Univ Evry, Univ Paris-Saclay, 91057 Evry, France
Search for more papers by this authorDr. Virgil Hélaine
Université Clermont Auvergne, CNRS, SIGMA Clermont, Institut de Chimie de Clermont-Ferrand, 63000 Clermont-Ferrand, France
Search for more papers by this authorDr. Tibor Liptaj
Slovak University of Technology, Faculty of Chemical and Food Technology, Radlinského 9, 81237 Bratislava, Slovakia
Search for more papers by this authorMartin Breza
Slovak University of Technology, Faculty of Chemical and Food Technology, Radlinského 9, 81237 Bratislava, Slovakia
Search for more papers by this authorAline Mariage
Génomique Métabolique, Genoscope, Institut François Jacob, CEA, CNRS, Univ Evry, Univ Paris-Saclay, 91057 Evry, France
Search for more papers by this authorLionel Nauton
Université Clermont Auvergne, CNRS, SIGMA Clermont, Institut de Chimie de Clermont-Ferrand, 63000 Clermont-Ferrand, France
Search for more papers by this authorDr. Mounir Traïkia
Université Clermont Auvergne, CNRS, SIGMA Clermont, Institut de Chimie de Clermont-Ferrand, 63000 Clermont-Ferrand, France
Search for more papers by this authorDr. Marcel Salanoubat
Génomique Métabolique, Genoscope, Institut François Jacob, CEA, CNRS, Univ Evry, Univ Paris-Saclay, 91057 Evry, France
These authors contributed equally to this work.
Search for more papers by this authorProf. Dr. Marielle Lemaire
Université Clermont Auvergne, CNRS, SIGMA Clermont, Institut de Chimie de Clermont-Ferrand, 63000 Clermont-Ferrand, France
These authors contributed equally to this work.
Search for more papers by this authorCorresponding Author
Dr. Christine Guérard-Hélaine
Université Clermont Auvergne, CNRS, SIGMA Clermont, Institut de Chimie de Clermont-Ferrand, 63000 Clermont-Ferrand, France
These authors contributed equally to this work.
Search for more papers by this authorCorresponding Author
Dr. Véronique de Berardinis
Génomique Métabolique, Genoscope, Institut François Jacob, CEA, CNRS, Univ Evry, Univ Paris-Saclay, 91057 Evry, France
These authors contributed equally to this work.
Search for more papers by this authorAbstract
Dihydroxyacetone phosphate (DHAP)-dependent rhamnulose aldolases display an unprecedented versatility for ketones as electrophile substrates. We selected and characterized a rhamnulose aldolase from Bacteroides thetaiotaomicron (RhuABthet) to provide a proof of concept. DHAP was added as a nucleophile to several α-hydroxylated ketones used as electrophiles. This aldol addition was stereoselective and produced branched-chain monosaccharide adducts with a tertiary alcohol moiety. Several aldols were readily obtained in good to excellent yields (from 76 to 95 %). These results contradict the general view that aldehydes are the only electrophile substrates for DHAP-dependent aldolases and provide a new C−C bond-forming enzyme for stereoselective synthesis of tertiary alcohols.
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