2-Adamantanone on deprotonation in the gas phase affords the corresponding β-enolate anion. It reacts with 1,1-dilithio-1-sila-2,3,4,5-tetraphenylsilole to yield 5-silafulvene. It was used in the synthesis of dispiro N-Boc-protected 1,2,4-trioxane and (+/-)-1-(adamantan-2-yl)-2-propanamine. 2-Adamantanone on deprotonation in the gas phase affords the corresponding β-enolate anion. It reacts with 1,1-dilithio-1-sila-2,3,4,5-tetraphenylsilole to yield 5-silafulvene. It was used in the synthesis of dispiro N-Boc-protected 1,2,4-trioxane and (+/-)-1-(adamantan-2-yl)-2-propanamine.