The trifluoromethyl tetrafluoro‐λ6‐sulfanyl (CF3SF4) group is both extraordinarily lipophilic and profoundly electron withdrawing, properties associated with polar hydrophobicity. Utilization of the CF3SF4 group to prepare novel materials or biologically active agents will not be possible without new methods for the synthesis of aliphatic CF3SF4‐substituted building blocks. To advance those studies, trichloromethanesulfenyl chloride was conveniently converted to trans‐trifluoromethyl tetrafluoro‐λ6‐sulfanyl chloride (CF3SF4Cl) by oxidative chlorofluorination. Triethylborane‐promoted addition reactions of trans‐CF3SF4Cl to substituted olefins and alkynes yielded a variety of new materials. Those addition products were subsequently transformed to CF3SF4‐substituted carboxylic acids, CF3SF4‐substituted ketones, and a CF3SF4‐substituted aldehyde.

Substituted alkenyl aryl tetrafluoro-λ(6) -sulfanes have been prepared by the direct addition of readily accessible chlorotetrafluorosulfanyl arenes to primary alkynes. Substitution of an apical fluorine of the pentafluorosulfanyl group enables modulation of the reactivity of this little explored functional group while at the same time facilitating the direct investigation of aryl substituent effects on the aryl tetrafluorosulfanyl-substituted products.

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Substituted alkenyl aryl tetrafluoro‐λ6‐sulfanes have been prepared by the direct addition of readily accessible chlorotetrafluorosulfanyl arenes to primary alkynes. Substitution of an apical fluorine of the pentafluorosulfanyl group enables modulation of the reactivity of this little explored functional group while at the same time facilitating the direct investigation of aryl substituent effects on the aryl tetrafluorosulfanyl‐substituted products.

Photochemical initiation of polymerization by visible or broadband ultraviolet irradiation of a mixture of 1,4‐(bis‐chlorotetrafluoro‐λ6‐sulfanyl) benzene and 1,4‐diethynyl benzene forms light responsive polymers. The novel polymers have a trans‐tetrafluoro‐λ6‐sulfanyl (tetrafluorosulfanyl, SF4) group backbone and are sensitive to electron beam (EB) and extreme ultraviolet (EUV) irradiation. Both EB lithography and EUV contrast experiments demonstrate the sensitivity of the polymer films to short wavelength irradiation.