Abstract Enantiomerically pure triflones R 1 CH (R 2) SO 2 CF 3 have been synthesized starting from the corresponding chiral alcohols via thiols and trifluoromethylsulfanes. Key steps of the syntheses of the sulfanes are the photochemical trifluoromethylation of the thiols with CF 3 Hal (Hal= halide) or substitution of alkoxyphosphinediamines with CF 3 SSCF 3. The deprotonation of RCH (Me) SO 2 CF 3 (R= CH 2 Ph, iHex) with nBuLi with the ...