A series of pyrazolo[3,4-b]pyrrolo[3,4-d]pyridine derivatives was synthesized via catalyst-free bi-component and one-pot reactions of 5-aminopyrazoles, DMF-DMA (or TMOF) and N-arylmaleimides in xylene as solvent. This protocol showed advantages of milder reaction conditions, easier work-up, shorter reaction times and good yields, over other approaches tested. Keywords: Aminopyrazoles, DMF-DMA, TMOF, maleimides, pyrazolopyrrolopyridines, Aza-Diels-Alder reaction.