Abstract Bicyclo orthoesters and amide acetals were prepared from the corresponding triols or diethanolamines using α, α-difluoroalkylamines. The reaction proceeded under milder conditions than conventional methods. 4-tert-Butyl-1-(4-ethynylphenyl) trioxabicyclo [2.2. 2] octane, a new class of insecticide, was prepared from a triol in three steps using a difluoroalkylamine.