Abstract The stereochemistry of catalytic phosphorylation of 1-(perfluoroalkyl)-ω-(trialkylsilyl) alkan-1-ols with pentavalent phosphorus acid monochlorides (phosphonochloridates, methyl (phenyl) phosphinic chloride, and phosphorochloridates) was studied. The effects of the structures of alcohols and phosphorylating agents on the degree of the reaction diastereoselectivity were investigated. Methylphosphonochloridates were found to react ...