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.

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Conversion of DBU from a nonrecoverable liquid base to a magnetically separable solid catalyst and its application for the diastereoselective multicomponent synthesis of 2-(N-carbamoylacetamide)-substituted 2,3-dihydrothiophenes.

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Polyethylene glycol-bonded triethylammonium L-prolinate ([PEG-TEA]LP) was prepared as a new, highly efficient, reusable and biodegradable amino acid-based ionic liquid catalyst using cheap and easily accessible starting materials. The [PEG-TEA]LP chemical...

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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.

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.