A Convenient and Efficient Method for Incorporation of Pentafluorosulfanyl (SF₅) Substituents into Aliphatic Compounds.

Abstract

Thio compounds P 0440A Convenient and Efficient Method for Incorporation of Pentafluorosulfanyl (SF 5 ) Substituents into Aliphatic Compounds. -SF 5 Cl as well as SF 5 Br smoothly undergo efficient addition to a variety of alkenes and alkynes under mild, free radical chain reaction conditions. The SF5Cl addition reactions are regiospecific, highly diastereoselective and relatively insensitive to a wide range of non-allylic functionalities.-(DOLBIER*, W. R. J.; AIT-MOHAND, S.; SCHERTZ, T. D.; SERGEEVA, T. A.; CRADLEBAUGH, J. A.; MITANI, A.; GARD, G. L.; WINTER, R. W.; THRASHER,

Relationships between the Properties of Families of Materials

“…The pentafluorosulfanyl (-SF 5 ) functional group is of recent interest (a) because of its similarity to and differences from the trifluoromethyl (-CF 3 ) group, (b) because of its potential use in biochemically active substances, 11 and (c) because of new synthetic techniques for introducing the group to organic molecules. 12 Because there are relatively few known materials containing the pentafluorosulfanyl group, its effects on the physical properties of substances containing it are relatively unknown. The trifluoromethyl group is present in many more known materials, and it would be useful to understand the properties of the SF 5 -containing compounds based on knowledge of the properties of the CF 3 -containing compounds.…”

“…While we have found simple or linear relationships for a wide variety of other properties and a wide variety of families of materials, we here show just one more example. The pentafluorosulfanyl (−SF 5 ) functional group is of recent interest (a) because of its similarity to and differences from the trifluoromethyl (−CF 3 ) group, (b) because of its potential use in biochemically active substances, and (c) because of new synthetic techniques for introducing the group to organic molecules . Because there are relatively few known materials containing the pentafluorosulfanyl group, its effects on the physical properties of substances containing it are relatively unknown.…”

Recent Advances in the Synthesis and Medicinal Chemistry of SF5 and SF4Cl Compounds

“…The synthesis of alkyl and alkenyl SF 5 compounds via pentafluorosulfanylation of their alkenyl and alkynyl, respectively, precursors is largely based on the Dolbier method. 3…”

“…α-SF 5 ketones represent valuable building blocks for further chemical diversifications and applications, but, despite their potential usefulness, only few examples were reported until 2017. 34a b With the aim of establishing if the SF 5 group could efficiently direct the addition of water to a neighboring alkyne, Paquin et al described the first regioselective gold-catalyzed hydration of SF 5 -alkynes. 34c The latter were synthesized from the corresponding alkynes using the Dolbier’s protocol, followed by a base-promoted elimination.…”

“…Methods for the synthesis of SF 5 compounds can be classified depending on whether the substituent is carried by an aliphatic or by an aromatic/heteroaromatic carbon. For the former, the most utilized method is the Dolbier reaction, 3 which relies on both SF 5 Cl and SF 5 Br undergoing addition to alkenes and alkynes under mild free radical chain reaction, via triethylborane initiation at low temperature. For aromatic and heteroaromatic SF 5 compounds, the most utilized method is probably the Umemoto reaction, 2b which consists of two steps: first the treatment of the starting diaryl disulfide or aryl thiol with chlorine in the presence of an alkali metal fluoride, and then treatment of the resulting arylsulfur chlorotetrafluoride with a fluoride source, such as AgF, ZnF 2 , or HF.…”