Abstract
An effective carbonyl‐oxygen‐assisted transition‐metal‐free approach was developed for the one‐pot synthesis of 1,4‐diketones through the formal hydration of 4‐alkynones with complete regioselectivity under mild conditions. The reaction tolerates a wide range of functional groups, and the corresponding functionalized 1,4‐diketones were obtained in moderate to excellent yields (up to 94 %). Importantly, the complete regioselectivity was attributed to the fact that 2,3‐dihydrofuran intermediates were obtained as single products through the 5‐exo‐dig cyclization of 4‐alkynones; this was supported by control and isotope‐labeling experiments.
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