Organoseleno-Catalyzed Synthesis of α,β-Unsaturated α′-Alkoxy Ketones from Allenes Enabled by Se•••O Interactions

alpha,beta-Unsaturated alpha'-alkoxy ketones have been prepared under mild conditions from allenes using water as the oxygen source and without the necessity of metals. The organocatalytic oxygenation-rearrangement sequence displays an exquisite chemo-, stereo-, and site-selectivity as well as good functional group compatibility. DFT calculations suggest that stabilizing noncovalent Se center dot center dot center dot O interactions may be responsible for the observed reactivity.