10.1016/S0040-4039(00)87168-3
The research presents a novel synthetic method for creating 3-amino-2-alkenoates, which are valuable intermediates for synthesizing various heterocycles like pyridines, pyrimidines, indoles, and isothiazoles. These compounds also exhibit anti-inflammatory properties in some N-aroyl derivatives. The study explores the use of magnesium enolates of t-butyl (or ethyl) acetate and t-butyl propionate, which react with nitriles to produce 3-amino-2-alkenoates with Z configuration. The researchers initially attempted using lithium enolate of t-butyl acetate but found it ineffective due to the instability of the primary adduct and the inability of the lithium ion to incorporate the nitrile group. Instead, they successfully employed magnesium enolate derived from diisopropylamine and ethylmagnesium bromide, achieving efficient yields of the desired compounds. The procedure was applicable to various nitriles, although those with relatively acidic o-hydrogen atoms resulted in lower yields. Protected acetaldehyde cyanohydrins also yielded good results. The products were characterized by GLC and 1H-NMR spectroscopy, confirming their structures and configurations.