Dichlorination of (Z)-allylic trichloroacetates efficiently and stereoselectively generates the syn,syn hydroxydichloride stereotriad that is prevalent in the understudied polychlorinated sulfolipid class of natural products. Further, the dichlorination of a (Z)-allylic chlorohydrin affords with high selectivity a stereotetrad present in one of the chlorosulfolipids.