The mechanism of the gold(i)-catalyzed Meyer-Schuster rearrangement of 1-phenyl-2-propyn-1-olvia4-endo-digcyclization

With the aim of rationalizing the experimental counterion- and solvent-dependent reactivity in the gold(i)-catalyzed Meyer-Schuster rearrangement of 1-phenyl-2-propyn-1-ol, a computational mechanistic study unraveled the unexpected formation of a gold-oxetene intermediateviacommonly unfavorable 4-endo-digcyclization triggered by the counterion in low polarity solvents.