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

被引:80
作者
Espelt, L
Parella, T
Bujons, J
Solans, C
Joglar, J
Delgado, A
Clapés, P
机构
[1] CSIC, Inst Chem & Environm Res, Dept Peptide & Protein Chem, Barcelona 08034, Spain
[2] CSIC, Inst Chem & Environm Res, DBOC, RUBAM, Barcelona 08034, Spain
[3] CSIC, Inst Chem & Environm Res, Dept Surfactant Technol, Barcelona 08034, Spain
[4] Univ Autonoma Barcelona, Serv Ressonancia Magnet Nucl, Bellaterra, Spain
[5] Univ Barcelona, Fac Farm, Unitat Quim Farmaceut, E-08028 Barcelona, Spain
关键词
biotransformations; colloids; DHAP-dependent aldolases; iminocyclitols; lyases;
D O I
10.1002/chem.200304966
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The 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-l-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 NCbz aminopolyols thus obtained were submitted to catalytic intramolecular reductive amination to afford the corresponding iminocyclitols. Ibis 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).
引用
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页码:4887 / 4899
页数:13
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