The aryloxy triester phosphoramidate prodrug approach has been used with success in drug discovery. Herein, we describe the first application of this prodrug technology to the monophosphate derivative of the phosphoantigen HMBPP and one of its analogues. Some of these prodrugs exhibited specific and potent activation of Vγ9/Vδ2 T-cells, which were then able to lyse bladder cancer cells in vitro. This work highlights the promise of this prodrug technology in the discovery of novel immunotherapeutics.

Tethered bromomaleimides are described which undergo thiol conjugation and rapid regio- and stereoselective photocycloadditions to serve as disulfide staples; with the excited state intermediates observed by transient absorption spectroscopies.

Herein we report on photodecarboxylations of various substituted maleimides, resulting in an elimination reaction. Furthermore, we establish facile wavelength tunability through modulation of the maleimide double bond substituents. We envisage that these versatile reagents, which are readily constructed and diversified by nucleophilic substitution reactions on bromomaleimides, will offer new opportunities for triggered photorelease.