Sulfoximines as a Versatile Scaffold for Electrophilic Fluoroalkylating Reagents

Abstract

New electrophilic fluoroalkylating agents based on the sulfoximine skeleton as a common platform are described. We demonstrate the importance of the activating group, attached to the nitrogen, and its specificity for the fluorinated group to be delivered. As an application, a variety of unknown dichlorofluoro, bromodifluoro, and trifluoromethyl alkynes have been prepared using these reagents.

A Mild and Efficient Procedure for the N-Functionalization of S-Perfluoroalkylated Aryl Sulfoximines

“…For example, we have shown that in the case of electrophilic perfluoroalkylating reagents, the reactivity was specific to the fluorinated moiety being delivered. 11 Also, an investigation of the coupling reactions between compounds 2 and aryl iodides or bromides, induced by a copper catalyst, revealed an obvious difference with the non-halogenated derivatives. 16 During this study, we noticed that the quantities of catalyst required were greater than those used in the non-fluorinated series.…”

“…A large panel of different electrophiles was engaged in the reaction. The product N-acylated sulfoximines were isolated in good yields (74-100%) with benzyl ( [11][12][13]. All the products were stable and have been fully characterized.…”

“…8 Sulfoximine derivatives have been employed successfully for the electrophilic introduction of trifluoro-and monofluoromethyl moieties by Shibata, 9 difluoromethyl groups by Hu, 10 and bromodifluoro-and dichloromethyl by our group. 11 In 2012, Hu expanded the applications of perfluoroalkylated sulfoximines and showed that mono-and difluoromethyl derivatives were efficient reagents for the nucleophilic transfer of perfluorinated units. 12 In contrast to non-fluorinated sulfoximines, which have been studied extensively, 1 access to the S-perfluoroalkylated analogues was, since 1986, strictly limited to the efficient, but quite cumbersome, synthesis as described by Yagupolskii and co-workers.…”

The New Age of Electrophilic Perfluoro­alk­ylation Reactions

“…[57] Although the protocol of Shibata was nicely reproduced for the syntheses of 69 and 70, its extension to the preparation of compounds 77 and 78 gave very low yields. N-Functionalizations of these three sulfoximines with triflyl groups were achieved in good yields (Scheme 24), but the synthesis of the ammonium analogues proved more problematic.…”

Development of Shelf-Stable Reagents for Fluoro-Functionalization Reactions

“…15 Magnier reported an alternative method for the preparation of 10 by the Ritter-type reaction avoiding the use of explosive sodium azide. 34 The reagent 10 is now commercially available as Shibata reagent I. Figure 5.…”