Preparation and reactions of sulfonimidoyl fluorides

SuFEx Chemistry of Thionyl Tetrafluoride (SOF4) with Organolithium Nucleophiles: Synthesis of Sulfonimidoyl Fluorides, Sulfoximines, Sulfonimidamides, and Sulfonimidates

“…Finally,L ewis acid induced S À Fbond cleavage and asubsequent S À Cbond formation also gave sulfoximine III-14 from sulfonimidoyl fluoride II-3. [8] Aside from the sequential creation of SÀCl inkages,t he SuFEx reaction with heteroatom linkages has proved to be ar obust approach for diverse functionalization through SÀF handles.S ulfonimidates and sulfonimidamides have hitherto mainly been prepared from sulfonimidoyl chlorides,w hich are liable to hydrolysis and redox side reactions. [22,23] In Table 3, we demonstrate the modification of the natural products capsaicin, estrone,a nd (+ +)-d-tocopherol through DBU-promoted formation of SÀOl inks with sulfonimidoyl fluorides,giving the corresponding sulfonimidates in excellent yields and with good functional group tolerance.A sh ighlighted earlier in this manuscript, an N-alkyl substituent (IV-1)g enerally makes the Scenter less electrophilic in comparison with an N-aryl substituent (IV-2, IV-3), and therefore requires excess DBUf or full conversion from the corresponding sulfonimidoyl fluorides.A gain, DBUa lso serves as ap romising base in the reaction with secondary amines (showcased in example V-1).…”

“…First reported by Johnson and coworkers in 1983, sulfonimidoyl fluorides have been conventionally prepared by the treatment of sulfonimidoyl chlorides with afluoride source ( Figure 1C). [8] However,because of the harsh reaction conditions and al engthy de novo four-step process,o nly ac onfined number of derivatives were available. [1,9] Our protocol is complementary,b ut has significant advantages owing to its straightforward, rapid, and modular operation.…”

Optical Activation and Utilization of Compounds Containing Chiral Sulfur Centers

“…While the majority of these iminations proceed with retention of configuration at sulfur, Cram and Day found that N-sulfinyl-/?-toluenesulfonamide reacts with (R)-methy\-ptolyl sulfoxide in the presence of pyridine with inversion (98% stereospecific) [Eq. This ester was reacted with an excess of methyllithium to furnish a good yield of (5) Alternatively, the treatment of sulfonimidoyl chlorides with fluoride ion (sodium fluoride in acetonitrile, tetrabutylammonium fluoride in acetonitrile, or potassium fluoride in acetonitrile containing 18-crown-6) results in good to excellent yields of the corresponding sulfonimidoyl fluorides (89). This problem was circumvented by prior conversion of the sulfonimidoyl chlorides to sulfonimidoates (71b, 87).…”

SuFEx Chemistry of Thionyl Tetrafluoride (SOF4) with Organolithium Nucleophiles: Synthesis of Sulfonimidoyl Fluorides, Sulfoximines, Sulfonimidamides, and Sulfonimidates

“…First reported by Johnson in 1983, sulfonimidoyl fluorides were conventionally prepared by the treatment of sulfonimidoyl chlorides with a fluoride source (Figure 1C). [8] Because of the harsh reaction conditions and a lengthy de novo four-step process, however, only a confined number of derivatives were available. [1, 9] Our protocol is complementary, but has significant advantages due to its straightforward, rapid and modular operation.…”

“…Finally, a Lewis acid induced S–F bond cleavage and subsequent S–C bond formation also gave sulfoximine III-14 from sulfonimidoyl fluoride II-3 . [8] …”