Pentafluorosulfanyl (SF 5 )-containing compounds and corresponding analogs are a highly valuable class of fluorine-containing building blocks owing to their unique properties. The reason for that is the set of peculiar and tremendously beneficial characteristics they can impart on molecules once introduced onto them. Despite this, their application in distinct scientific fields remains modest, given the extremely harsh reaction conditions needed to access such compounds. The recent synthetic approaches via SÀ F, and CÀ SF 5 bond formation as well as the use of SF 5containing building blocks embody a "stairway-to-heaven" loophole in the synthesis of otherwise-inaccessible chemical scaffolds only a few years ago. Herein, we report and evaluate the properties of the SF 5 group and analogs, by summarizing synthetic methodologies available to access them as well as following applications in material science and medicinal chemistry since 2015.
With glycerol being a bulk waste product, the interest in converting it to other value‐added products is steadily increasing. A scalable continuous flow process was developed for the synthesis of glycerol carbonate (2‐GLC) from glycerol and dimethyl carbonate on a hydroxide functional resin. High conversion and selectivity were obtained while the residence times were typically shorter than 10 min. Continuous production of 2‐GLC was achieved in high throughput and with improved processing metrics, creating the foundations for a production level process.
Sulfur(VI)-fluoride exchange (SuFEx) chemistry, an all-encompassing term for substitution events that replace fluoride at an electrophilic sulfur(VI), enables the rapid and flexible assembly of linkages around a S VI core. Although a myriad of nucleophiles and applications works very well with the SuFEx concept, the electrophile design has remained largely SO 2 -based. Here, we introduce S�N-based fluorosulfur(VI) reagents to the realm of SuFEx chemistry. Thiazyl trifluoride (NSF 3 ) gas is shown to serve as an excellent parent compound and SuFEx hub to efficiently synthesize mono-and disubstituted fluorothiazynes in an ex situ generation workflow. Gaseous NSF 3 was evolved from commercial reagents in a nearly quantitative fashion at ambient conditions. Moreover, the mono-substituted thiazynes could be extended further as SuFEx handles and be engaged in the synthesis of unsymmetrically disubstituted thiazynes. These results provide valuable insights into the versatility of these understudied sulfur functionalities paving the way for future applications.
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Pyrazine derivatives R 0550Synthesis of Novel Functionalized Symmetric Bi-2(1H)-pyrazinones. -The homo-coupling of pyrazinones (I) based on a Suzuki-type cross-coupling protocol is used for the synthesis of novel bipyrazinones (II). The coupling is carried out either under conventional heating or under microwave irradiation. -(DE BORGGRAEVE*, W. M.; APPUKKUTTAN, P.; AZZAM, R.; DEHAEN, W.; COMPERNOLLE, F.; VAN DER EYCKEN, E.; HOORNAERT, G.; Synlett 2005, 5, 777-780; Dep. Chem., Kathol. Univ. Leuven, B-3001 Leuven, Belg.; Eng.) -R. Staver 33-175
Pyrazine derivatives R 0550 Expanding the Substitution Pattern of 2(1H)-Pyrazinones via Suzuki and Heck Reactions. -A wide range of pyrazinones are available under these conditions. They are useful peptidomimetics. -(AZZAM, R.; DE BORGGRAEVE, W. M.; COMPERNOLLE*, F.; HOORNAERT, G. J.; Tetrahedron 61 (2005) 16, 3853-3862; Lab. Org. Synth., Dep. Chem., Univ. Leuven, B-3001 Leuven, Belg.; Eng.) -Jannicke 34-220
The sulfur-fluorine partnership occupies a privileged position in fluorine chemistry given the functional versatility that it imparts to organic structures. Despite this, available methodologies to forge S-F bonds are limited compared to C-F bond formation. Here, we describe a synthetic protocol that selectively enables the oxidative halogenation of aliphatic, aromatic, and heteroaromatic thiols to their corresponding SF4Cl, SO2F and SF3 derivatives. Selective oxidation of thiols to either S(IV)-F or S(VI)-F compounds is achieved by employing bench-stable calcium hypochlorite as chlorine surrogate (CLOgen), in the presence of KF as fluoride source. DFT calculations provided insight into the mechanistic aspects of the transformation and rationalized the observed isomeric preference towards the SF4Cl derivatives. Ultimately, this glovebox-free method selectively dispatches three classes of compounds upon reaction condition finetuning. Furthermore, first-in-class transformations are reported, including the preparation of aliphatic SF4Cl intermediates, their transformation into aliphatic sulfur pentafluoride analogs, and posttransformations that allow accessing highly complex SF4-bridged scaffolds.
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