Chemoselective Hydro(Chloro)pentafluorosulfanylation of Diazo Compounds with Pentafluorosulfanyl Chloride

Abstract

Pentafluorosulfanyl chloride (SF 5 Cl) is the most prevalent reagent for the incorporation of SF 5 group into organic compounds. However, the preparation of SF 5 Cl often relies on hazardous reagents and specialized apparatus. Herein, we described a safe and practical synthesis of a bench-stable and easy-to-handle solution of SF 5 Cl in nhexane under gas-reagent-free conditions. The synthetic application of SF 5 Cl was demonstrated through the unprecedented reaction with diazo compounds. The chemoselective hydroand chloropentafluorosulfanylations of a-diazo carbonyl compounds were developed in the presence of K 3 PO 4 or copper catalyst, respectively. These reactions provide a direct and efficient access to various a-pentafluorosulfanyl carbonyl compounds of high value for potential applications.Scheme 1. Preparation of a solution of SF 5 Cl in n-hexane.

When SF5 outplays CF3: effects of pentafluorosulfanyl decorated scorpionates on copper

“… 2,3 Furthermore, molecules with pentafluorosulfanyl groups are also becoming more accessible via effective and convenient routes. 4 A number of derivatization reactions of SF 5 -group containing molecules are also known. 3 a ,3 b ,4 e ,5…”

Oxidative Fluorination of Heteroatoms Enabled by Trichloroisocyanuric Acid and Potassium Fluoride

“…Moreover, in a relatively short time span, we have also begun to see exciting applications of TCICA/KF appear in the literature from several other laboratories following our initial report (for some examples, see Figure 7). [61, 62, 66, 72–74] …”

Oxidative Fluorination of Heteroatoms Enabled by Trichloroisocyanuric Acid and Potassium Fluoride

“…Moreover, in a relatively short time span, we have also begun to see exciting applications of TCICA/KF appear in the literature from several other laboratories following our initial report (for some examples, see Figure 7). [61,62,66,[72][73][74] As the exploratory inorganic fluorine chemistry detailed herein was founded on a pragmatic approach to synthesis at the inception, we hope our efforts sit comfortably enough to the organic-inorganic interface of fluorine chemistry to see applications of molecules containing heteroatom-fluorine bonds continue to blossom.…”

“…As we were developing our own strategy for userfriendly synthesis/use of SF 5 Cl on an as-needed basis, Qing reported an elegant solution in 2021 establishing a protocol that allows extraction of SF 5 Cl into hexanes solution directly ( � 0.10-0.15 M solution) so that SF 5 Cl never needs to be handled as a gas. [66] Between our discovery of a gas-reagentfree SF 5 Cl synthesis and Qing's optimization of the extraction procedure, exploring new applications in SF 5 radical chemistry and even designing/synthesizing new possible SF 5 transfer reagents now seem within reach. Moreover, several transformations have been developed in the past few years with SF 5 Cl that may become even more accessible with this ability to synthesize the reagent easily in house.…”