A new publication in Science from UC Berkeley scientists documents an unusual rearrangement of dihydrobenzofuran promoted by light. They leveraged this unusual rearrangement to develop a method for the isomerization of dihydrobenzofuran that allows for transfer of acyl functional groups to a different site in the molecule. Acyl transpositions are traditionally difficult, but the presented skeletal rearrangement strategy for functional group transposition circumvents these difficulties. The authors envision that this method could allow for rapid late-stage derivatization of small-molecule drug candidates.
When this unusual photochemical reactivity was first observed, it was unclear exactly what was occurring. The solution state NMR conducted in the PMRC facility gave the researchers the resources to determine exactly how the carbon atoms were moving relative to one another via solution state NMR, which provided key insight for how to leverage this rearrangement into the method.