Abstract:The polar hydrophobic trifluoromethyl-λ6-tetrafluorosulfanyl (CF3SF4) group effectively induces secondary structure in a heptapeptide in both polar and non-polar solvents.
“…With their unusual properties and the growing interest in SuFEx click chemistry, there has been a drive towards development of sulphur/fluorine-containing moieties [ [162] , [163] , [164] , [165] , [166] , [167] ]. The addition of complex sulphur and fluorine containing functional groups across olefins has been studied by Welch and co-workers [ 168 , 169 ]. To a protected alkene-containing amino acid ( 223 ) was added CF 3 SF 4 Cl in the presence of base, allowing for an SF 4 CF 3 moiety to be added across the alkene, giving compound 224 in 91 % ( Scheme 44 ).…”
“…With these amino acid building blocks in hand, they were then further elaborated into short peptides and the influence that the fluorinated moiety had on the adopted secondary structure was probed. Scheme 44 Access to an SF 4 CF 3 alkene amino acid, Welch and co-workers [ 169 ]. …”
“…With their unusual properties and the growing interest in SuFEx click chemistry, there has been a drive towards development of sulphur/fluorine-containing moieties [ [162] , [163] , [164] , [165] , [166] , [167] ]. The addition of complex sulphur and fluorine containing functional groups across olefins has been studied by Welch and co-workers [ 168 , 169 ]. To a protected alkene-containing amino acid ( 223 ) was added CF 3 SF 4 Cl in the presence of base, allowing for an SF 4 CF 3 moiety to be added across the alkene, giving compound 224 in 91 % ( Scheme 44 ).…”
“…With these amino acid building blocks in hand, they were then further elaborated into short peptides and the influence that the fluorinated moiety had on the adopted secondary structure was probed. Scheme 44 Access to an SF 4 CF 3 alkene amino acid, Welch and co-workers [ 169 ]. …”
“…Compared to the SF 5 group, the CF 3 SF 4 group occupies a larger volume (138.93 Å 3 for CF 3 SF 4 vs 102.96 Å 3 for SF 5 ) and has a greater lipophilicity [π p (CF 3 SF 4 ) = 2.13 vs π p (SF 5 ) = 1.23] and an equally strong electron-withdrawing ability [σ p (CF 3 SF 4 ) = 0.68 vs σ p (SF 5 ) = 0.68] . Consequently, the CF 3 SF 4 group has shown promising applications in biology and materials science. , So far, CF 3 SF 4 -containing compounds are rather limited, likely due to a lack of efficient and easily available methods for introducing the CF 3 SF 4 group …”
mentioning
confidence: 99%
“…4 Consequently, the CF 3 SF 4 group has shown promising applications in biology and materials science. 4,5 So far, CF 3 SF 4 -containing compounds are rather limited, likely due to a lack of efficient and easily available methods for introducing the CF 3 SF 4 group. 6 Among the reported methods for the introduction of the CF 3 SF 4 group into organic compounds, 7 the use of trifluoromethyltetrafluorosulfanyl chloride (CF 3 SF 4 Cl) as a trifluoromethyltetrafluorosulfanylating reagent was the mainstream protocol for accessing trifluoromethyltetrafluorosulfanylated aliphatic compounds.…”
mentioning
confidence: 99%
“…Previously, reactions of trans -CF 3 SF 4 Cl were limited to the atom-transfer radical addition (ATRA) with unsaturated compounds, such as alkenes and alkynes (Scheme a). , Recently, our group developed a new radical addition of SF 5 Cl to α-diazo carbonyl compounds . We envisaged that trans -CF 3 SF 4 Cl may also react with diazo compounds to afford α-CF 3 SF 5 -substituted ketones and esters (Scheme b).…”
trans-Trifluoromethyltetrafluorosulfanyl chloride
(trans-CF3SF4Cl) is a unique
reagent for the incorporation of the CF3SF4 group
into organic compounds. However, CF3SF4Cl was
prepared from hazardous reagents or formed as mixture of trans and cis isomers in low yield. Herein, a silver-promoted
selective synthesis of trans-CF3SF4Cl under safe gas-reagent-free conditions is described. Furthermore,
the synthetic application of trans-CF3SF4Cl is demonstrated through the new trifluoromethyltetrafluorosulfanylation
of α-diazo carbonyl compounds.
Alkyne hydroamination is an effective approach for the production of enamines and enaminecontaining N-heterocycles. However, stereoselectivity control is a considerable challenge in this reaction because of the electronic repulsion between an incoming nitrogen lone pair and the alkyne π-system. Herein, we propose a methodology involving β-regio-and Zselective alkyne hydroamination by using tetrafluoro-λ 6sulfanyl (SF 4 ) alkynes under superbasic, naked anion conditions. The reaction is compatible with a wide variety of N-heterocycles, including indoles, carbazoles, pyrazoles, and imidazoles, and selectively furnishes SF 4linked Z-vinyl enamines with β-regioselectively. Moreover, the method can be extended to the β-and Zcontrolled, base-mediated alkyne hydrophenoxylation with phenols to provide SF 4 -linked Z-vinyl ethers in high yields. As the SF 4 unit has attracted attention as a bioisostere for alkynes, p-benzenes, bicyclo[1.1.1]pentyl (BCP) groups, and cubanes in medicinal chemistry, this chemistry represents an effective approach to creating novel drug candidates incorporating SF 4 -containing molecules.
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