Herein is introduced the application of “super-electron-donor”(SED) 2-azaallyl anions in a tandem reduction/radical cyclization/radical coupling/aromatization protocol that enables the rapid construction of isoquinolines. The value of this transition-metal-free method is highlighted by the wide range of isoquinoline ethyl amines prepared with good functional group tolerance and yields. An operationally simple gram scale synthesis is also conducted, confirming the scalability.

An efficient synthesis of tryptamines is developed. Indole structures were constructed using 2-iodoaryl allenyl amines as electron acceptors and radical cyclization precursors. Radical–radical coupling of indolyl methyl radicals and azaallyl radicals led to the tryptamine derivatives. The utility and versatility of this method are showcased by the synthesis of 22 examples of tryptamines in ≤88% yield. In each case, indole formation is accompanied by in situ removal of the Boc protecting group.