Magnesium ester enolates reactions with nitriles

It is useful to note that Hiyama and Kobayashi have reported successful reactions of nitriles with a magnesium ester enolate (Scheme 23), whereas the corresponding lithium ester enolate failed to react. 

The condensation reaction of ester enolates with nitriles are an important general source of alkenyl-P-amino acids. In a simple example, the reaction of t-bulyl acetate with magnesium diisopropylamide and then propanenitrile led to /-butyl 3-amino-hex-2-enoate, 4.81. In addition, /-butyl 3-aminobut-2-enoate (66%), 3-amino-4-methylpent-2-enoate (74%), 3-amino-4,4-dimethylpent-2-enoate (43%), 3-amino-4-phenyIpent-2-enoate (25%) and other 4-aryl and 2-alkyl- ubstituted alkenylamino... 

New syntheses of enamino-ketones by the ring-opening of isoxazoles with samarium di-iodide and with pentacarbonyliron, by the reaction of 2-alkyl-thiomethyl-3-alkylthioacrylophenones with amines, and by the intramolecular photoarylation of A -[2-(haloaryl)ethyl]-(3-enaminones, of enamino-diketones by the reaction of (3-chlorosulphonic acid chlorides with amines and by amino-methylenation of cyclic (3-dicarbonyl compounds, and of enamino-esters by aminomethylenation of esters and lactones and by the reaction of nitriles with magnesium enolates have been reported. 

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