As novel porous organic polymers with thiourea linkages, POP-TUs were successfully synthesized with tris(4-aminophenyl) amine (TAA) and 1,4-phenylene diisothiocyanate (PDT) under different conditions. The as-synthesized POP-TUs possess distinctly different morphological characteristics and can effectively catalyze the Michael reaction of trans-β-nitrostyrenes to diethyl malonate. Particularly, the POP-TU-2-catalyzed Michael reaction can proceed smoothly even using an ultralow catalyst dosage of 0.03 mol %, whose turnover number (TON) and turnover frequency (TOF) can reach up to 2700 and 25 h-1, respectively. Besides, POP-TU-2 also exhibits excellent recyclability and reusability. Only 2% decline in the isolated yield was found after five consecutive runs. This work shows a significant improvement over previously reported thiourea-based catalysts and can offer an effective strategy for developing highly efficient heterogeneous organocatalysts.
Keywords: Michael reaction; heterogeneous catalysis; organocatalysts; porous organic polymers; thiourea.