New sulfuryl fluoride-derived alkylating reagents for the 1,1-dihydrofluoroalkylation of thiols

Abstract

Herein, we report a new method for the one-pot synthesis of 1,1-dihydrofluoroalkyl sulfides by bubbling sulfuryl fluoride (SO2F2) through a solution of the corresponding alcohol and thiol.

Traceless N‐Polyfluoroalkylation of Weakly Nucleophilic Nitrogen Containing Compounds

“…The difference in reactivity between DBU and DIPEA in sulfuryl fluoride-mediated fluoroalkylation reactions was previously observed by Sammis et al for thiols. [21] The use of DBU as a base was shown to lead to the formation of a symmetric bis(trifluoroethyl)sulfate intermediate that selectively reacts with thiols in the presence of other nucleophilic functional groups such as an amine, alcohol or carboxylic acid. [21] Consistent with this report, the bis(trifluoroethyl)sulfate intermediate generated with DBU also showed weak reactivity with saccharin 1 a as nucleophile.…”

“…Compared to the use of triflates that generate triflic acid, which is persistent and belongs to the newly defined PFAs, this synthesis attractively achieves traceless N ‐alkylation. Sulfuryl fluoride‐mediated fluoroalkylation methods have been applied to alkylamines or thiols, but weaker N ‐nucleophiles such as anilines have proven to be poor substrates under the reported conditions [18a,21] . Our group has begun to investigate SO 2 F 2 ‐mediated N ‐polyfluoroalkylation of challenging substrates that are highly relevant to agrochemical and pharmaceutical applications.…”

Emerging electrolytes with fluorinated solvents for rechargeable lithium-based batteries

“…Deoxofluorination is a critical method to transform alcohols into aliphatic fluorides. [165][166][167] Various deoxofluorination reagents, including Et 2 NSF 3 (DAST), FluoLead, XtalFluor, and (MeOCH 2 CH 2 ) 2 NSF 3 (Deoxofluor), have been exploited to date. 168 The mechanism of deoxofluorination is also a typical nucleophilic substitution, in which the reagents are susceptible to nucleophilic attack by activated hydroxy and accompanied by Walden inversion of substrates during the reaction process (Fig.…”

New Chemical Transformations Involving SO2F2‐Mediated Alcohol Activation

“…Our study started by using the poorly nucleophilic saccharin moiety ( N =10.78 according to Mayr's scale) [71] as a model substrate for the optimization of the reaction conditions. This optimization mainly focused on the choice of the base, which shows significant effect on the reaction outcome for most SO 2 F 2 ‐alkylation processes reported to date [59,62,65,72] . Whereas DBU was very efficient for the N ‐alkylation of imino‐thiazolidinone moieties, [62] we were surprised to see that the same conditions gave only traces of the desired alkylated saccharin.…”