Synthesis and Reactivity of 5-Substituted Furfuryl Carbamates via Oxanorbornadienes

Furfuryl carbamates are labile and require care to be accessed by activating furfuryl alcohols. An alternative oxanorbornadiene (OND)-based strategy is presented for the preparation of 5-R-substituted furfuryl carbamates via the reactions of amines with intermediate OND carbonates. The resulting OND carbamates, which are stable for several months, undergo thiol mediated retro-Diels-Alder reaction to deliver the desired furfuryl carbamates in a single flask. Conditions for the selective hydrolysis of furfuryl carbamates in the presence of tert-butyloxycarbonyl (Boc) groups were identified, and it was shown that furfuryl carbamates can be used as a prodrug handle.