Improved Buchner reaction selectivity in the copper-catalyzed reactions of ethyl 3-arylmethylamino-2-diazo-3-oxopropanoates

Abstract

Ethyl 3-alkyl(arylmethyl)amino-2-diazo-3-oxopropanoates (diazo amidoacetates) generate generally both cyclohepta[c]pyrrolones (Buchner products) and β-lactams (1,4-insertion products), and show obvious N-substituent-controlled chemoselectivity between the intramolecular Buchner reaction and aliphatic 1,4-C-H insertion under the catalysis of copper salts. The less steric N-alkyl substituents in the amide moiety generally favor the aliphatic 1,4-C-H insertion, while the more steric N-alkyl substituents generally favor the Buchner reaction. Compared with rhodium and ruthenium-catalyzed conditions, the current copper-catalyzed conditions improved the Buchner reaction selectivity of ethyl 3-alkyl(arylmethyl)amino-2-diazo-3-oxopropanoates.