Duncan M. Gill

Decoupling Deprotonation from Metalation: Thia‐Fries Rearrangement

Label-enabled: Studies with 2H-, 18O-, and 34S-labeled aryl triflates show that lithium diisopropylamide-mediated thia-Fries rearrangement proceeds through an irreversible orthou2005deprotonation (see scheme; DIPA=diisopropylamine, LDA=lithium diisopropylamide). In contrast, orthou2005metalation results exclusively in the generation of a benzyne.

Stereocontrolled access to optically-enriched oxabispidines

A range of chiral, optically-enriched bicyclic oxabispidines were prepared from (S)-(-)-2,3-epoxypropylphthalimide using an efficient sequence featuring a stereocontrolled intramolecular Mannich reaction as the key transformation.

On the preparation of ortho-trifluoromethyl phenyl triflate.

In contrast to an earlier report advocating a copper-mediated trifluoromethylation of ortho-iodophenyl triflate, ortho-trifluoromethyl phenyl triflate may be prepared simply by reacting the corresponding phenol with triflic anhydride in the presence of a nucleophilic catalyst and stoichiometric base.