Assessment of TEMPO as a Thermally Activatable Base Generator and Its Use in Initiation of Thermally-Triggered Thiol-Michael Addition Polymerizations.

ABSTRACT: We present a thermally initiated thiol-Michael reaction based on initiation via the temperature-dependent thiol-TEMPO oxidation-reduction reaction. In the presence of a thiol, 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO, pK a = 5.5) is reduced to produce a much stronger base, i.e., tetramethylpiperidine (TMP, pK a = 11.4) in a temperature dependent process. This oxidation-reduction process is dramatically accelerated at elevated temperature, which allows for thermally controlled initiation of the base-catalyzed thiol-Michael addition reaction and potentially other base-catalyzed reaction systems. Several critical factors that affect base generation from TEMPO reduction were investigated via systematic variation of reaction conditions including the solvent, temperature, and the thiol type a

SUBMITTER: Zhang X 

PROVIDER: S-EPMC6366629 | biostudies-literature | 2018 Aug

REPOSITORIES: biostudies-literature