Synthesis of Trifluoromethyl Tetrafluoro‐λ 6 ‐sulfanyl‐Substituted Alkenes, Ketones, and Acids: Polar Hydrophobic Building Blocks

The trifluoromethyl tetrafluoro‐λ 6 ‐sulfanyl (CF 3 SF 4 ) group is both extraordinarily lipophilic and profoundly electron withdrawing, properties associated with polar hydrophobicity. Utilization of the CF 3 SF 4 group to prepare novel materials or biologically active agents will not be possible without new methods for the synthesis of aliphatic CF 3 SF 4 ‐substituted building blocks. To advance those studies, trichloromethanesulfenyl chloride was conveniently converted to trans ‐trifluoromethyl tetrafluoro‐λ 6 ‐sulfanyl chloride (CF 3 SF 4 Cl) by oxidative chlorofluorination. Triethylborane‐promoted addition reactions of trans ‐CF 3 SF 4 Cl to substituted olefins and alkynes yielded a variety of new materials. Those addition products were subsequently transformed to CF 3 SF 4 ‐substituted carboxylic acids, CF 3 SF 4 ‐substituted ketones, and a CF 3 SF 4 ‐substituted aldehyde.