Benzenetellurinyl acetate or trifluoroacetate in combination with ethyl carbamate effected aminotellurinylation of olefins in chloroform under reflux in the presence of boron trifluoride etherate to give ethyl [(2-phenyltelluro)alkyl]carbamates in high yields after reduction with hydrazine hydrate. This reaction was extended to cyclofunctionalization of olefinic carbamates into nitrogen heterocycles.