Synthesis of Tetrakis(amino)ethylene-Derived Organic Reductants via Thermal Decomposition of Tris(amino)methanes

Tetrakis(amino)ethylene (TAE)-based reductants are valuable in organic transformations, such as cross-electrophile coupling, but are not widely utilized due to their high cost and complicated syntheses. Here, we report the one-pot synthesis of TAE-derived organic reductants via thermal decomposition of tris(amino)methanes. Specifically, the neat reaction of <i>N</i>,<i>N</i>-dimethylformamide dimethylacetal (DMF-DMA) with pyrrolidine or piperidine generates tetrakis(pyrrolidino)ethylene (TPyE) or tetrakis(piperidino)ethylene (TPiE) in one pot through the <i>in situ</i> generation of a tris(amino)methane intermediate. The synthesis and thermal decomposition of other tris(amino)methanes were also investigated.