Fluoride‐Catalyzed Deblocking: A Route to Polymeric Urethanes

Abstract

We report af luoride-catalyzed deblocking of urethanes as "blocked" isocyanates.O rganic and inorganic sources of fluoride ion proved effective for deblocking urethanes and for converting polyurethanes to small molecules. Distinct from conventional deblocking chemistry involving organometallic compounds and high temperatures,the method we describe is metal-free and operates at or slightly aboveroom temperature.T he use of fluorescent blocking agents enabled visual and spectroscopic monitoring of blocking/deblocking reactions,a nd the selected conditions proved applicable to urethanes containing avariety of blocking groups.The method additionally enabled aone pot deblocking and polymerization with a,w-diols.O verall, this deblocking/polymerization strategy offers aconvenient and efficient solution to problems that have limited the breadth of applications of polyurethane chemistry.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under https://doi.