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2-Keto-3-Deoxy-L-Rhamnonate Aldolase (YfaU) as Catalyst in Aldol Additions of Pyruvate to Amino Aldehyde Derivatives

AuthorsHernández Sánchez, Karel ; Gómez, Ariadna; Joglar, Jesús; Bujons, Jordi; Parella, Teodor; Clapés Saborit, Pere
Pyruvate aldolases
Aldol reaction
Amino Aldehydes
Amino acids
Asymmetric Catalysis
Issue Date11-May-2017
CitationAdvanced Synthesis and Catalysis 2017
AbstractAbstract. 4-Hydroxy-2-ketoacid derivatives are versatile building blocks for the synthesis of amino acids, hydroxy carboxylic acids and chiral aldehydes. Pyruvate aldolases are privileged catalysts for a straightforward access to this class of ketoacid compounds. In this work, a Class II pyruvate aldolase from Escherichia coli K-12, 2-keto-3-deoxy-L-rhamnonate aldolase (YfaU), was evaluated for the synthesis of amino acid derivatives of proline, pipecolic acid, and pyrrolizidine-3-carboxylic acid. The aldol addition of pyruvate to N-protected amino aldehydes was the key enzymatic aldol addition step followed by catalytic intramolecular reductive amination. The corresponding N-Cbz-amino-4-hydroxy-2-ketoacid (Cbz=benzyloxycarbonyl) precursors were obtained in 51%-95% isolated yields and enantioselectivity ratios from 26:74 to 95:5, with chiral -substituted N-Cbz-amino aldehydes. (S)-N-Cbz-amino aldehydes gave aldol adducts with preferentially (R)-configuration at the newly formed stereocenter, whereas the contrary is true for (R)-N-Cbz-amino aldehydes. Addition reactions to achiral amino aldehydes rendered racemic aldol adducts. Molecular models of the pre-reaction ternary complexes YfaU-pyruvate enolate-acceptor aldehyde were constructed to explain the observed stereochemical outcome of the reactions. Catalytic reductive amination of the aldol adducts yielded 4-hydroxy-2-pipecolic acid, and unprecedented C5 substituted 4-hydroxy proline and pyrrolizidine-3-carboxylic acid derivatives.
Publisher version (URL)10.1002/adsc.201700360
Appears in Collections:(IQAC) Artículos
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