The enol phosphate 2,2-dichloro-1-(trichloromethyl)ethenyl diethyl phosphate (1), easily available by a Perkow reaction between hexachloroacetone and triethyl phosphite, reacts with sodium trifluoroethoxide/trifluoroethanol in the presence of cyclic 5-membered 1,3-dienes to furnish alpha,alpha,alpha',alpha'-tetrachloro-substituted[3.2.1]bicyclic ketones 2. A [4+3] cycloaddition of a tetrachloro-oxyallyl intermediate is postulated.