Abstract When treated with KOH under phase-transfer catalysis or with Bu t OK, 3-substituted (alkyl or phenyl) 1, 1, 3-tribromo-1-fluoropropanes 1a—c exclusively generate previously unknown (alk-1-ynyl) fluorocarbenes 5a—c, which react with olefins to give 1-(alk-1-ynyl)-1-