title: Expedient synthesis of C-aryl carbohydrates by consecutive biocatalytic benzoin and aldol reactions.
abstract: The introduction of aromatic residues connected by a C-C bond into the non-reducing end of carbohydrates is highly significant for the development of innovative structures with improved binding affinity and selectivity (e.g., C-aril-sLex). In this work, an expedient asymmetric "de novo" synthetic route to new aryl carbohydrate derivatives based on two sequential stereoselectively biocatalytic carboligation reactions is presented. First, the benzoin reaction of aromatic aldehydes to dimethoxyacetaldehyde is conducted, catalyzed by benzaldehyde lyase from Pseudomonas fluorescens biovar I. Then, the α-hydroxyketones formed are reduced by using NaBH4 yielding the anti diol. After acetal hydrolysis, the aldol addition of dihydroxyacetone, hydroxyacetone, or glycolaldehyde catalyzed by the stereocomplementary D-fructose-6-phosphate aldolase and L-rhamnulose-1-phosphate aldolase is performed. Both aldolases accept unphosphorylated donor substrates, avoiding the need of handling the phosphate group that the dihydroxyacetone phosphate-dependent aldolases require. In this way, 6-C-aryl-L-sorbose, 6-C-aryl-L-fructose, 6-C-aryl-L-tagatose, and 5-C-aryl-L-xylose derivatives are prepared by using this methodology.
authors: Biotransformation and Bioactive Molecules Group, Instituto de Química Avanzada de Cataluña, IQAC-CSIC. Jordi Girona 18-26, 08034 Barcelona (Spain), Fax: (+34) 932045904.
authors: Karel
authors: K
authors: Hernández
authors: Teodor
authors: T
authors: Parella
authors: Jesús
authors: J
authors: Joglar
authors: Jordi
authors: J
authors: Bujons
authors: Martina
authors: M
authors: Pohl
authors: Pere
authors: P
authors: Clapés
mesh_terms: D000446:Aldehyde-Lyases / Q000737:chemistry* / Q000378:metabolism; D000447:Aldehydes / Q000737:chemistry*; D001573:Benzoin / Q000737:chemistry*; D055162:Biocatalysis; D002241:Carbohydrates / Q000138:chemical synthesis* / Q000737:chemistry; D004098:Dihydroxyacetone / Q000737:chemistry*; D004926:Escherichia coli / Q000737:chemistry* / Q000378:metabolism; D005636:Fructosephosphates / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure
chemical_list: D000447:Aldehydes; D002241:Carbohydrates; D005636:Fructosephosphates; C027618:fructose-6-phosphate; D000446:Aldehyde-Lyases; C059416:benzaldehyde lyase; C022526:rhamnulose-1-phosphate adolase; D001573:Benzoin; D004098:Dihydroxyacetone
keywords: CC bond formation; aldolases; benzaldehyde lyase; carbohydrates; enzyme catalysis