Hydroxylation of nitro-(pentafluorosulfanyl)benzenes via vicarious nucleophilic substitution of hydrogen

Oxidative nucleophilic substitution of hydrogen in nitro(pentafluorosulfanyl)benzenes with alkyl Grignard and lithium reagents

“…The combined yields were good and the products were separated by column chromatography. The regioselectivity of the nucleophilic addition (5:6 ratio) ranged from 1:1 for i-PrMgBr to 2:1 for MeLi, which is much lower than in previously described VNS reactions with more stabilized (less reactive) carbon or oxygen nucleophiles to 2 [6,7]. VNS amination of 2 with Me 3 N + NH 2 I À proceeds exclusively Table 1 Optimization of n-propylmagnesium bromide (3a) addition to 1-nitro-4-(pentafluorosulfanyl)benzene (1) in position ortho relative to the nitro group [8].…”

“…Additionally, a patent literature described a two-step conversion of diaryl disulfides to SF 5 -aromatics [3]. While S E Ar of 1 or 2 is very limited (nitration of 2 to give 3,5-dinitro(pentafluorosulfanyl)benzene in 33% yield was reported) [4], we have recently described S N Ar of the nitro group in compounds 1 and 2 with alkoxides and thiolates [5] and vicarious nucleophilic substitution (VNS) of the hydrogen with carbon [6], oxygen [7] and nitrogen [8] nucleophiles. Reduction of the nitro group in 1 or 2 to (pentafluorosulfanyl)anilines followed by acylation, S E Ar halogenation or diazotation (with follow-up reactions) provided number of SF 5 -benzene derivatives [2b,9].…”

Single crystal X-ray structural features of aromatic compounds having a pentafluorosulfuranyl (SF5) functional group

“…Compounds 1-3 were obtained from Apollo Scientific without further purification; compounds 4 [19], 5 [20], 6 [19], 7 [21], 8 [22], and 9 [21] were prepared according to the literature method. The crystal structure data were collected by using a Rigaku SCX-Mini diffractometer (Mercury 2 CCD) at -148℃with graphite-monochromated Mo-Kα radiation (λ= 0.71073 Å) for compounds 1-4, 6, 7 and 9; a Mercury diffractometer (Mercury 70) at -148℃ for compound 5, and the St Andrews Robotic diffractometer (Saturn70 CCD) at -148℃ [23][24][25] for compound 8.…”

Synthesis of pentafluorosulfanyl (SF5) containing aromatic amino acids

“…There are a variety of ways to access alkyl [ [15] , [16] , [17] , [18] ] and aryl [ [19] , [20] , [21] , [22] , [23] , [24] ] pentafluorosulfanyl compounds. Despite the advances in the utility and synthesis of SF 5 building blocks, the ability to introduce them into peptides has so far been limited [ 25 ].…”