Homolytic Alkylation of Enamines by Electrophilic Radicals

Article abstract of DOI:10.1021/jo00011a007

The electrophilic radicals R* = p-O2NC6H4CH2* or Me2C(NO2)* add readily to CH2=C(NMe)2 to yield RCH2C(NMe2)2* which undergoes electron transfer with p-O2NC6H4CH2Cl or Me2C(NO2)2 to regenerate R*.Hydrolysis yields p-O2NC6H4CH2CONMe2 and Me2C=CHC(NMe2)2(1+), respectively. p-Nitrobenzyl radicals add readily to N-pyrrolidino- or N-morpholino-1-cycloalkenes to yield after hydrolysis the α-(p-nitrobenzyl)cycloalkanones.Photostimulated alkylation of N-pyrrolidino-1-cycloalkenes by Me2C(NO2)2 is not observed although in competitive reactions between the enamine and Me2C=NO2Li, the product from attack of Me2C(NO2)* upon the eneamine double bond is formed.The N-pyrrolidino-1-cycloalkenes are more reactive toward p-O2NC6H5CH2 than their morpholine analogues.