Regio- and stereoselective addition of Brønsted acids to yndiamides: Synthesis of N,O,N- and N,S,N-trisubstituted ketene acetals

Yndiamides, N,N-disubstituted alkynes, are versatile building blocks for the synthesis of nitrogen-containing organic molecules. Unlike ynamides, relatives that are inherently polarized by a single nitrogen substituent, their pseudo-symmetric nature renders regioselective reactions challenging. Here we report investigations into the regioselective addition of Brønsted acids to non-symmetric yndiamides, a reaction that delivers N,O,N- and N,S,N-trisubstituted ketene acetals with excellent regio- and stereoselectivity.

Dithiocarbamate-mediated controlled copolymerization of ethylene with cyclic ketene acetals towards polyethylene-based degradable copolymers

In this article, degradable polyethylene (PE)-based copolymers containing ester units in the backbone were prepared through the hybrid copolymerization of ethylene and cyclic ketene acetals (CKAs) mediated by dithiocarbamate successfully.

Unraveling the History and Revisiting the Synthesis of Degradable Polystyrene Analogues via Radical Ring-Opening Copolymerization with Cyclic Ketene Acetals

Degradable analogues of polystyrene are synthesized via radical ring-opening (co)polymerization (rROP) between styrene and two cyclic ketene acetals, namely 2-methylene-1,3-dioxepane (MDO) and 5,6-benzo-2-methylene-1,3-dioxepane (BMDO). This approach periodically inserts ester bonds throughout the main chain of polystyrene, imparting a degradation pathway via ester hydrolysis. We discuss the historical record of this approach, with careful attention paid to the conflicting findings previously reported. We have found a common 1H NMR characterization error, repeated throughout the existing body of work. This misinterpretation is responsible for the discrepancies within the cyclic ketene acetal (CKA)-based degradable polystyrene literature. These inconsistencies, for the first time, are now understood and resolved through optimization of the polymerization conditions, and detailed characterization of the degradable copolymers and their corresponding oligomers after hydrolytic degradation.