Synthesis of pyridine trans-tetrafluoro-λ⁶-sulfane derivatives via radical addition

Abstract

Pyridine-trans-SF4-alkenes or -alkanes have been synthesized for the first time via the radical addition reactions of pyridine-trans-SF4Cl to alkynes or alkenes in good to high yields.

An eccentric rod-like linear connection of two heterocycles: synthesis of pyridine trans-tetrafluoro-λ6-sulfanyl triazoles

“…Finally, reaction of the pyridine SF 4 -alkynes 3 with azides 4 under thermal Huisgen 1,3-dipolar cycloaddition conditions provided the eccentric, three-dimensionally unique trans -SF 4 linked pyridine and triazole derivatives 5 in high yields ( Scheme 1 ). 11 While a few examples of aryl-SF 4 -aryl were reported, 3 this is the first example for the synthesis of heteroaryl-SF 4 -heteroaryl systems. An aryl-SF 4 -heteroaryl system was also accessed by the method.…”

“… 2 On the other hand, the tetrafluoro-λ 6 -sulfane (tetrafluorosulfanyl, SF 4 ) moiety, with equally potent functionality, has not been exploited enough and is highly underdeveloped. 3 The SF 4 moiety not only has unique physiochemical properties, which make it suitable as a unit of liquid crystals, 1 , 3 but also has interesting geometric features that enable it to connect two independent functional groups via the central hypervalent sulfur atom in either the cis or trans configuration of R-SF 4 -R′ ( Fig. 1a ).…”

“… 3 , 4 Due to the octahedral geometry of the R-SF 4 -R′ moiety, the trans -SF 4 configuration has the ability to function as a building block in the construction of linear structures via its axial bonds, which makes the trans -SF 4 configuration highly significant. 3 , 4 The rod-like connection by the trans -SF 4 unit potentially suggests new approaches for designing novel pharmaceuticals, while also leading to sought-after fluorine-containing drug candidates. As an extension of our research on fluorine-containing heterocycles, 5 we were interested in the development of a novel method to connect two heterocyclic rings via a rod-like linear linker.…”

Die SF5‐Gruppe zugänglicher gemacht: Eine gasfreie Synthese von Aryl‐Tetrafluor‐λ6‐Sulfanyl‐Chloriden

“…Neben der Anwendung in der SF 5 ‐Chemie haben die Laboratorien von Welch und Shibata zeigen können, dass Aryl‐SF 4 Cl‐Intermediate auch für die Synthese von ungewöhnlicheren Aryl‐SF 4 R‐Verbindungen (R=Alkyl‐, Alkenyl‐, Alkynyl‐) genutzt werden können. Diese Verbindungen sind gegenüber weiteren Modifikationen und gegenüber Säulenchromatographie stabil, insofern sie elektronenziehende Substituenten tragen.…”

Studies of Halogen Bonding Induced by Pentafluorosulfanyl Aryl Iodides: A Potential Group of Halogen Bond Donors in a Rational Drug Design

“…[36][37][38][39][40][41] More and more examples of biologically active SF5-contaning drug candidates have been reported in recent years ( Figure 1c). [34,[37][38][39][40][41] Extending our research to the design and synthesis of SF5-containing biologically attractive molecules [42][43][44][45][46][47][48][49][50][51][52][53][54] and a halogen bonding research program, [55,56] we are interested in aryl iodides 1a-d consisting of SF5-group(s) in the benzene ring as potential drug fragments capable of halogen bonding, in particular, 3,5-bis-pentafluorosulfanyl iodobenzene 1d (Figure 1d).…”