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Title

Stereoselective aldol additions catalyzed by dihydroxyacetone phosphate-dependent aldolases in emulsion systems: preparation and structural characterization of linear and cyclic iminopolyols from aminoaldehydes

AuthorsEspelt, Laia; Parella, Teodor; Bujons Vilàs, Jordi ; Solans, Conxita ; Joglar Tamargo, Jesús ; Delgado, Antonio; Clapés Saborit, Pere
KeywordsBiotransformations
Colloids
DHAP-dependent aldolases
Iminocyclitols
Lyases
Issue Date19-Sep-2003
PublisherWiley-Blackwell
CitationChemistry - a European Journal 9(20): 4887-4899 (2003)
AbstractThe potential of dihydroxyacetone phosphate (DHAP)-dependent aldolases to catalyze stereoselective aldol additions is, in many instances, limited by the solubility of the acceptor aldehyde in aqueous/co-solvent mixtures. Herein, we demonstrate the efficiency of emulsion systems as reaction media for the class I fructose-1,6-bisphosphate aldolase (RAMA) and class II recombinant rhamnulose-1-phosphate aldolase from E. coli (RhuA)-catalyzed aldol addition between DHAP and N-benzyloxycarbonyl (N-Cbz) aminoaldehydes. The use of emulsions improved the RAMA-catalyzed aldol conversions by three to tenfold relative to those in conventional DMF/water mixtures. RhuA was more reactive than RAMA towards the N-Cbz aminoaldehydes regardless of the reaction medium. With (S)- or (R)-Cbz-alaninal, RAMA exhibited preference for the R enantiomer, while RhuA had no enantiomeric discrimination. The linear N-Cbz aminopolyols thus obtained were submitted to catalytic intramolecular reductive amination to afford the corresponding iminocyclitols. This reaction was diastereoselective in all cases examined; the face selectivity was controlled by the stereochemistry of the newly formed hydroxyl group originating from the aldehyde. Characterization of the resulting iminocyclitols allowed the assessment of the diastereoselectivity of the enzymatic aldol reactions with respect to the N-protected aminoaldehyde. RAMA formed single diastereoisomers from N-Cbz-glycinal and from both enantiomers of N-Cbz-alaninal, while 14 % of the epimeric product was observed from N-Cbz-3-aminopropanal. Diastereoselectivity from RhuA was lower than that observed from RAMA. Interestingly, a single diastereoisomer was formed from (S)-Cbz-alaninal, whereas only a 34 % diastereomeric excess was observed from its enantiomer (i.e., (R)-Cbz-alaninal).
Description13 pages, 2 figures, 6 schemes, 5 tables.-- PMID: 14562306 [PubMed].-- Printed version published Oct 17, 2003.-- Supporting information available at: http://www.wiley-vch.de/contents/jc_2111/2003/f4966_s.pdf
Publisher version (URL)http://dx.doi.org/10.1002/chem.200304966
URIhttp://hdl.handle.net/10261/20179
DOI10.1002/chem.200304966
ISSN0947-6539
E-ISSN1521-3765
Appears in Collections:(IDAEA) Artículos
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