EPR studies of radical hydrogen abstraction reactions of N-heterocyclic carbene (NHC) complexes of alkenylboranes bearing two ester substituents revealed not the expected boraallyl radicals but instead isomeric 1,2-oaxborole radicals. Such radicals are new, and DFT calculations show that they arise from the initially formed boraallyl radicals by a rapid, exothermic 5-endo cyclization. These spectroscopic and computational discoveries prompted a series of preparative experiments that provided access to a novel family of robust NHC-boralactones. A one-pot procedure was developed to access the boralactones directly from an NHC-borane (NHC-BH3) and dimethyl acetylenedicarboxylate.