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Volumn 9, Issue 20, 2003, Pages 4887-4899

Stereoselective Aldol Additions Catalyzed by Dihydroxyacetone Phosphate-Dependent Aldolases in Emulsion Systems: Preparation and Structural Characterization of Linear and Cyclic Iminopolyols from Aminoaldehydes

Author keywords

Biotransformations; Colloids; DHAP dependent aldolases; Iminocyclitols; Lyases

Indexed keywords

ALDEHYDES; AMINATION; CATALYSIS; CHARACTERIZATION; EMULSIONS; MIXTURES; SOLUBILITY; SOLVENTS;

EID: 0142228971     PISSN: 09476539     EISSN: None     Source Type: Journal    
DOI: 10.1002/chem.200304966     Document Type: Article
Times cited : (92)

References (86)
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    • note
    • Swern oxidation of alcohol 3 furnished 7 with lower optical purity than that obtained with IBX.
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    • note
    • Observation of the emulsions with optical microscopy prior to the reaction (i.e., immediately before addition of the enzyme) revealed the following features: at 51 mM aldehyde (30mM DHAP) the emulsions formulated with tetradecane and hexadecane were highly concentrated water-in-oil-type emulsions while the one formulated with squalane was a diluted oil-in-water emulsion; at 340 mM aldehyde (120 mM DHAP) all emulsions were diluted oil-in-water emulsions. During the progress of the enzymatic reaction, the highly concentrated water-in-oil emulsions became more fluid, changing progressively to diluted oil-in-water emulsions near the end of the reaction. From these preliminary observations it appears that the type of emulsion did not influence the reaction performance.
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    • note
    • -1) or aminoaldehyde 5 (50 mM) at pH 6.9. In the blank experiment, a 15 % degradation of DHAP was observed after 24 h. In the presence of either RAMA or aldehyde, 30% degradation was detected after 24 h.
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    • note
    • A possible diastereoisomer of 9 or 13 (15 %) was detected but its relative configuration could not be identified unequivocally due to overlapping signals in the NMR spectra.
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    • (Eds.: J. B. Lambert, Y. Takeuchi), VCH, Weinheim
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    • note
    • At low temperatures (285 K), distinctive signals were observed in the high-field proton NMR spectrum for the corresponding linear 10 and the two five-membered ring conformers. Unfortunately, it was not possible to freeze the equilibrium between the two cyclic conformers and therefore the stereochemistry at C-2 could not be determined unequivocally. Moreover, the NMR spectra revealed the existence of only one of the two possible cyclic diastereoisomers, indicating that attack of the secondary amine on the ketone carbonyl exhibited face selectivity.
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    • note
    • Hydrogenation at atmospheric pressure for 2 h afforded the corresponding cyclic imine sugars.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.