A novel protocol for the highly selective N-monoalkylation of the sulfamate ester moiety has been developed. This reaction proceeded efficiently using alkyl halides, benzyl halides and α-halo ketones as the electrophile in the presence of KF-Al 2 O 3 as a cost-effective and robust catalyst. This approach provides new access to N-monoalkylated Topiramate (anticonvulsant drug) derivatives which are potentially of great importance in medicinal chemistry. O O O O O OSO 2 NH 2 O O O O O OSO 2 NR 2 O O O O O OSO 2 NHR RX, KF-Al 2 O 3 acetonitrile, 80ºC Topiramate N-monoalkyl Topiramate (major) N,N'-dialkyl Topiramate (minor) +