Organocatalyzed Anionic Ring-Opening Polymerizations of <i>N</i>‑Sulfonyl Aziridines with Organic Superbases

The anionic ring-opening polymerizations (AROPs) of <i>N</i>-sulfonyl aziridines, in the presence of organic superbases including phosphazene (<i>t</i>-Bu-P<sub>4</sub>), Verkade’s base (P­(<i>i</i>-PrNCH<sub>2</sub>CH<sub>2</sub>)<sub>3</sub>N, TiPP), DBU, MTBD, and <i>N</i>,<i>N</i>,<i>N</i>′,<i>N</i>′-tetramethylguanidine (TMG), using <i>N</i>-benzyl-<i>p</i>-toluenesulfonamide (BnN­(H)­Ts) as initiator were explored to produce metal-free poly­(sulfonylaziridine)­s. Among the superbases used, the catalytic activity was found directly proportional to their basicity. Remarkably, <i>t</i>-Bu-P<sub>4</sub> and TiPP gave a living/controlled AROP of 2-methyl-<i>N</i>-tosylaziridine (TsMAz), where <i>t</i>-Bu-P<sub>4</sub> performed better, affording the metal-free and well-defined poly­(sulfonylaziridine)­s with high molar masses (<i>M</i><sub>n</sub>(SEC) > 30 kg mol<sup>–1</sup>) and low dispersities (<i><i>Đ</i></i> < 1.10) in 3.5 h. For the less reactive monomers of 2-methyl-<i>N</i>-ethylsulfonyl aziridine (EsMAz) and 2-phenyl-<i>N</i>-tosylaziridine (TsPhAz), <i>t</i>-Bu-P<sub>4</sub> showed the same excellent catalytic efficiency (30 equiv, conv. > 95%, 5 h). The organocatalyzed AROP allowed the use of lower catalyst (<i>t</i>-Bu-P<sub>4</sub>) loading than the amount of initiator (BnN­(H)­Ts), but the propagating polymer chains were as many as the number of equivalents of the introduced initiators, which could lower the loading of catalyst used to amounts as low as 0.05 mol %.