Reaction of dicarbomethoxycarbene with thiophene derivatives.
Photolysis of derivatives of dimethylmalonate thiophene-S,C-ylide provides dicarbomethoxycarbene, which can react with thiophene to form dimethyl (2-thienyl)malonate. By generation of dicarbomethoxycarbene from the dibenzothiophene-based ylide in neat thiophene, it is shown that the thienylmalonate is not a product of rearrangement of the thiophene ylide, in contrast to thermolysis results. Formation of the thienylmalonate is suppressed by substitution of any sort in the 2- and 5-positions on the thiophene and by substitution with an electron-withdrawing substituent.
Jenks
William S
WS
Department of Chemistry, Iowa State University, Ames, Iowa 50011-3111, USA. wsjenks@iastate.edu
Heying
Melanie J
MJ
Stoffregen
Stacey A
SA
Rockafellow
Erin M
EM