Asymmetric Synthesis of (<i>R</i>)‐3‐Hydroxy‐2‐methylpropanoate (‘Roche Ester’) and Derivatives <i>via</i> Biocatalytic CC‐Bond Reduction

Abstract

Abstract Enoate reductases from the ‘old yellow enzyme’ family were employed for the asymmetric bioreduction of methyl 2‐hydroxymethylacrylate and its O ‐allyl, O ‐benzyl and O ‐TBDMS derivatives to furnish ( R )‐configurated methyl 3‐hydroxy‐2‐methylpropionate products in up to &gt;99% ee Variation of the O ‐protective group had little influence on the stereoselectivity, but a major impact on the reaction rate.