The synthesis of allenyl boronates is an important yet challenging topic in organic synthesis. Reported herein is an NHC-gold-catalyzed 1,3-H shift toward allenyl boronates synthesis from simple propargylic B(MIDA)s. Mechanistic studies suggest dual roles of the boryl moiety in the reaction: to activate the substrate for isomerization and at the same time, to prevent the allene product from further isomerization. These effects should be a result of α-anion stabilization and α-cation destabilization conferred by the B(MIDA) moiety, respectively. The NHC-Au catalyst, which is commercially available, is also found to be reactive in alkyne-to-1,3-diene isomerization reactions in an atom-economic and base-free manner.
Keywords: 1,3-diene; NHC-Au; alkyne; allene; isomerization.
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