Biocatalytic Synthesis of Nitrile-Bearing All-Carbon Quaternary Stereocenters

The synthesis of all-carbon quaternary stereocenters containing nitriles is a very important and challenging subject in organic chemistry. We used a biocatalytic approach under mild conditions to obtain new derivatives of these scaffolds by oxidation of catechols by Myceliophthora thermophila laccase (Novozym 51003) to afford o-quinones and 1,4-addition of a series of carbon nucleophiles containing tertiary alkyle nitriles to these intermediates. Using this approach, alpha-cyano carbonyls bearing a quaternary stereocenter were also prepared. Finally, the yields for the prepared compounds were 72-94%.