Synthesis and further use of SF5-alkynes as platforms for the design of more complex SF5-containing products

The hydrothiolation of TIPS-CΞC-SF5 – Charting the chemical space of beta-SF5 vinyl sulfides

“…Surprisingly, aromatic amino (3) and hydroxy (10) substituents did not interfere with the reaction at all but resulted in superior yields due to its strongly electron donating character. In contrast, moderately electron withdrawing substituents like CF3 (12,13,17) as well as unprotected carboxylic acids ( 25) caused a slight reduction in yield. The even stronger -accepting nitro group was found to significantly harm the reaction when in close proximity to the reaction site (11) (33%) (Figure 2) while it was smoothly tolerated in a remote position (20).…”

“…SF5 acetylenes recently have been shown to be versatile building blocks in chemical synthesis. [12] Very recently, we reported the hydroamination of TIPS-CC-SF5 (1) in a proof of principle study to showcase the versatility of this molecule. [13] A broad variety of so far elusive -SF5 enamines could be obtained in moderate to excellent yields employing a rather simple bench-top procedure.…”

Regio‐ and Stereoselective Hydroelementation of SF5‐Alkynes and Further Functionalizations.

“…However, synthetic routes to SF 5 compounds with structural diversity remain highly challenging and rely mainly on two general methods: the direct radical pentafluorosulfanylation of alkenes, alkynes, diazo ketones or [1.1.1]propellane, [15] or the oxidative fluorination of aromatic thiols, disulfide or derivatives [16] . SF 5 ‐alkynes are readily accessible substrates which can be used in various transformations, such as cycloadditions, heterocyclic synthesis and hydrofunctionalization [17] . Great discoveries are also under investigation with the closely related R‐SF 4 ‐alkynes another class of promising SF n subunits [18] .…”

Expanding Radical Chloropentafluorosulfanylation of Alkynes

“…10 SF 5 -Alkynes are central in downstream functionalizations toward a wide range of heterocyclic and acyclic compounds (Figure 1A). 11 SF 5 -Alkynes are typically obtained in a two-step sequence from terminal alkynes by chloropentafluorosulfanylation with SF 5 Cl followed by HCl elimination with the aid of a base (Figure 1B). Ethynylbenziodoxolone reagents are also substrates for the reaction of SF 5 Cl under blue light irradiation.…”

“…Besides, the SF 5 group can be built from thiols and disulfides by oxidative fluorination to afford SF 5 -(het)­aromatics . SF 5 -Alkynes are central in downstream functionalizations toward a wide range of heterocyclic and acyclic compounds (Figure A) . SF 5 -Alkynes are typically obtained in a two-step sequence from terminal alkynes by chloropentafluorosulfanylation with SF 5 Cl followed by HCl elimination with the aid of a base (Figure B).…”