Bicyclo[3.2.1]oct-2-ene undergoes hydrogen–deuterium exchange through allyl and vinyl carbanionic intermediates under strongly basic conditions,tert-BuO−/tert-BuOD)at 185 °C. Only allylic exchange had been observed in previous studies withtert-BuO−/DMSO. Since the 2-tert-butoxybicyclo[3.2.1]octanes are stable under these conditions an addition–elimination sequence cannot account for exchange at C-3. The relative rates of exchange at C-2, -3, and -4, and the stereoselectivity at the allylic site were determined by2H nmr. For comparison, the rate of olefinic exchange in bicyclo[2.2.2]octene was also measured.