Desymmetrization of 7-silylcycloheptatriene through consecutive dihydroxylation and acyl-nitroso cycloaddition of the resulting diene moiety is described. Dihydroxylation occurred anti relative to the resident silicon group in line with previous observations made in the cyclohexadiene series. In contrast, the subsequent acyl-nitroso cycloaddition occurred with poor regiocontrol but good level of diastereocontrol syn to the bulky silyl substituent. The resulting cycloadducts were then elaborated further to provide a straightforward entry toward aminocycloheptitols in ten steps from commercially available tropylium salts.
