Abstract: | The reactions of carbethoxycarbene (:CH2-CO2Et, 2) with several acyclic enaminones (RCOCH=CR1NHR2, 3) lead to the unexpected formation of 2-Me, 3-CO2Et, 4-H, 5-R1-pyrroles 4 . Structural variations of the enaminones show that the structural fragments C(3)-CO2Et and C(2)-Me are provided by 2 and that the fragment C(5)-R1NHR2 originates from the enaminones 3 , while the RCO group from 3 is eliminated during the course of reaction. Reactions with cyclic and nitrogen-hindered enaminones do not lead to pyrrole formation but occur by simple insertion of 2 to the Cα-H bond. |