Unsymmetrical 2,5-dialkylpyrrolidines via reductive amination of 1,4-diketones
作者:Tappey H. Jones、James B. Franko、Murray S. Blum、H.M. Fales
DOI:10.1016/s0040-4039(00)71506-1
日期:1980.1
Reductive amination of 1,4-diketones with sodium cyanoborohydride and ammonium acetate produced 2,5-dialkylpyrrolidines in good yield and permitted inclusion of side chain unsaturation. The compounds were found in ants of the genus Monomorium.
Intramolecular aminopalladation of alkynylamines gave intermediary alkenylpalladium compounds that hydrolyzed and isomerized to thermodynamically stable cyclic imines. Treatment of 3-alkynylamines with a catalytic amount of PdCl2(MeCN)2 gave exclusively 1-pyrrolines in good yields; 5-alkynylamines afforded 2,3,4,5-tetrahydropyridines selectively. Treatment of 4-alkynylamines with Pd(II) afforded mixtures of both 5- and 6-membered cyclic imines. Applications to the synthesis of some naturally occurring alkaloids are also described.