Application of high-pressure conditions enables enantioselective Michael-type addition of dialkyl malonates to β-arylethenesulfonyl fluorides. The reaction is efficiently catalyzed with 5 mol % of tertiary amino-thiourea at 9 kbar. Chiral alkanesulfonyl fluorides are formed in yields of up to 96% and enantioselectivities of up to 92%. Functionalization of the adducts via sulfur fluoride exchange (SuFEx) reaction and desulfonylative cyclization is demonstrated.