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Volumn 9, Issue 16, 1998, Pages 2901-2913

Deracemization of compounds possessing a sec-alcohol or -amino group through a cyclic oxidation-reduction sequence: A kinetic treatment

Author keywords

[No Author keywords available]

Indexed keywords

ALCOHOL; AMINE;

EID: 0032555561     PISSN: 09574166     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0957-4166(98)00306-1     Document Type: Article
Times cited : (50)

References (52)
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    • In biocatalyzed reactions, the ratio of asymmetrizations versus kinetic resolutions is ∼1:4, database Faber, ∼9000 entries.
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    • E.e.=93.75% after four cycles; however, for an e.e. of 100%, an infinite number of cycles is required in theory.
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    • This can be conveniently explained by different paths of various gradient leading to a hilltop, the gradient determines the length of each path to reach the top
    • This can be conveniently explained by different paths of various gradient leading to a hilltop, the gradient determines the length of each path to reach the top.
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    • The term 'theoretical turnover' indicates the theoretical equivalents of reagents needed if oxidation and reduction are considered as 'ideal' reactions. In practice, however, the amounts required will be larger because excess reagent(s) may be needed in order to drive the reaction towards completion and/or due to decomposition of reagents during undesired side reactions
    • The term 'theoretical turnover' indicates the theoretical equivalents of reagents needed if oxidation and reduction are considered as 'ideal' reactions. In practice, however, the amounts required will be larger because excess reagent(s) may be needed in order to drive the reaction towards completion and/or due to decomposition of reagents during undesired side reactions.
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    • Alternatively, the Poe-scale can be used. The Poe-value corresponding to a time-value can be easily calculated through the e.e. at a given point of the reaction
    • Alternatively, the Poe-scale can be used. The Poe-value corresponding to a time-value can be easily calculated through the e.e. at a given point of the reaction.
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    • No maximum for P is observed if the amount of reducing agent is below the theoretical turnover. In this case, the process is disrupted by termination of the reverse reaction through lack of reducing agent
    • No maximum for P is observed if the amount of reducing agent is below the theoretical turnover. In this case, the process is disrupted by termination of the reverse reaction through lack of reducing agent.
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    • In order to reduce the Tht down to the absolute minimum (Tht=1), absolute selectivity (E=∞) is required.
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    • 2 carbon atoms), the process is linked to oxidation and reduction
    • 2 carbon atoms), the process is linked to oxidation and reduction.
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    • note
    • In principle, redox-systems comprising three types of chiral centers may be envisaged: (i) sec-alcohol/ketone [EC 1.1.3.X], (ii) sec-amine/imine [EC 1.4.3.X] and (iii) alkane/alkene [EC 1.3.3.X]. For the latter system, however, no feasible enantioselective biocatalytic oxidation system has been described to date.
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    • note
    • 2+ or non-heme iron are involved.
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