Synthesis of Branched‐Chain Sugars with a DHAP‐Dependent Aldolase: Ketones are Electrophile Substrates of Rhamnulose‐1‐phosphate Aldolases. (30th March 2018)

• Record Type: Journal Article
• Authors: Laurent, Victor; Darii, Ekaterina; Aujon, Angelina; Debacker, Marine; Petit, Jean‐Louis; Hélaine, Virgil; Liptaj, Tibor; Breza, Martin; Mariage, Aline; Nauton, Lionel; Traïkia, Mounir; Salanoubat, Marcel; Lemaire, Marielle; Guérard‐Hélaine, Christine; de Berardinis, Véronique
• Is Part Of: Angewandte Chemie. Volume 130:Number 19(2018)
• Page Start: 5565
• Page End: 5569
• Publication Date: 2018-03-30
• Subjects: Aldolasen -- Biokatalyse -- Carboligation -- Tertiäre Alkohole -- Verzweigte Zucker; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201712851
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: 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.