Desymmetrizing dinitrile substrates

Desymmetrization of dinitrile substrates using nitrile-active enzymes like NHases to get a chiral compound has been known about for ages, (Turner and Sugai & Ohta published early papers on this in 1993).

A nice later example of this is a biocatalytic synthesis of a (S)-methylDOPA precursor by Sugai and Ohta again:-

Realization of the synthesis of a,a-disubstituted carbamylacetates and cyanoacetates by either enzymatic or chemical functional group transformation, depending upon the substrate specificity of Rhodococcus amidase by Masahiro Yokoyama, Mieko Kashiwagi, Masakazu Iwasaki, Ken-ichi Fuhshuku, Hiromichi Ohta and Takeshi Sugai in Tetrahedron Asymmetry doi:10.1016/j.tetasy.2004.04.047

In the recent book “Practical Methods for Biocatalysis and Biotransformations” edited by Whittall and Sutton, there is a section on desymmetrization using nitrile active enzymes (though two are whole cell methods and the last is use of a Codexis nitrilase) written by Wijdeven, Kielbasinski and Rutjes (Section 5.5, p186-189).