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Synthesis of Branched‐Chain Sugars with a DHAP‐Dependent Aldolase: Ketones are Electrophile Substrates of Rhamnulose‐1‐phosphate Aldolases
Author(s) -
Laurent Victor,
Darii Ekaterina,
Aujon Angelina,
Debacker Marine,
Petit JeanLouis,
Hélaine Virgil,
Liptaj Tibor,
Breza Martin,
Mariage Aline,
Nauton Lionel,
Traïkia Mounir,
Salanoubat Marcel,
Lemaire Marielle,
GuérardHélaine Christine,
de Berardinis Véronique
Publication year - 2018
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201712851
Subject(s) - dhap , aldolase a , electrophile , chemistry , phosphate , biochemistry , fructose bisphosphate aldolase , dihydroxyacetone phosphate , stereochemistry , enzyme , catalysis
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.