Glutaronitrile

A. Nucleophilic Attack on Carbon. —(/) Activated Olefins. A study of triarylphosphine-catalysed dimerization of acrylonitrile to 2-methylene-glutaronitrile (26) and 1,4-dicyano-l-butene (27) has established a balance between phosphine nucleophilicity and protolytic strength of the solvent. The reaction of methyl vinyl ketone with triphenylphosphine in triethyl-silanol gave only 3-methylene-2,6-heptadienone (28). 

Bergeron, S., Chaplin, D.A., Edwards, J.H. et al. (2006) Nitrilase-catalyzed desymmetrization of 3-hydroxy-glutaronitrile preparation of a statin side-chain intermediate. Organic Process Research Development, 10, 661-665. 

Glutaronitrile, 3-hydroxy-, 46, 48 Glycerol chlorohydrin, 46, 24 Glycine (-butyl ester, 45, 47 conversion to acetamidoacetone, 45,1 Glyoxal, phenyl-, 48,109 Glyoxals from esters and the potassium salt of dimethyl sulfoxide, 48, 112... 

Desymmetrization is not restricted to a single class of enzyme. For example, Madrell et reported the gram-scale preparation of a key intermediate of the lovastatin lactone through the desymmetrization of 3-(benzyloxy)glutaronitrile using whole cells from Brevibacterium R312. The transformation occurs via a dual nitrile hydratase/amidase-catalysed hydrolysis to afford acid in 65 % yield and 88 % ee (Scheme 1.49). 

Glutaronitrile reacted with sulfur monochloiide to afford isothiazolyl-dithiazolium chloride 146 by an unknown mechanism (2002CC1872 Scheme 76). 

PC propylene carbonate NMO 3-methyl-2-oxazolidinone TBAI tetrabutylammonium iodide AN acetonitrile PN propionitrile GN glutaronitrile MAN methoxyacetonitrile MPN 3-methoxypropionitrile TBP tert-butylpyridine HMIml l-hexyl-3-methylimidazolium iodide DMPIml 1,2- dimethyl-3-propy-limidazolium iodide SOC Sumitomo Osaka Cement Co. Ltd. 

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