NADH Mimics on Diacetone-D-glucose: Stereoselective Biomimetic Reduction of Benzoylformate and Interpretation of Chirality Transfer Deduced by Molecular Orbital Approach

Article abstract of DOI:10.1016/0040-4020(95)00305-R

We have prepared novel NADH mimics, in which the 1,4-dihydronicotinamide structure is connected to the diacetone-D-glucose molecule via its C-1 nitrogen, e.g. compound 1a, and 1b, and through the amide bond, e.g. compound 2-6, and analyzed their ability to stereoselective reduction of methyl benzoylformate.Although NADH mimics 1-3 and 6 turned out to be less effective in chirality transfer toward methyl benzoylformate, much higher chirality transfer was observed in the reactions with the compounds (4 and 5) possesing free hydroxyl groups at 5',6'-position of furanose.Importance of an additional intramolecular coordinating substitutent to bivalent metal ion has been demonstrated in enhancing the stereoselectivity in the reduction of benzoylformate with such NADH mimics.To materialize these observation, transition-states of the hydride transfer from 1-methyl-1,4-dihydronicotinamide to methyl benzoylformate in the presence of magnesium (II) ion were calculated by semi-empirical molecular orbital method, MNDO-PM3.Also discussed in this paper is a general chirality transfer mechanism deduced from the theoretical transition-state modeling.

Full text of DOI:10.1016/0040-4020(95)00305-R

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Evaluation Only. Created with Aspose.PDF. Copyright 2002-2021 Aspose Pty Ltd.

Evaluation Only. Created with Aspose.PDF. Copyright 2002-2021 Aspose Pty Ltd.