Selectivity Controlled Hydroamination of Alkynes to Sulfonyl Fluoride Hubs: Development and Application

Abstract

A hydroamination of unactivated alkynes and lithium bis­(fluorosulfonyl)­imide (LiN­(SO2F)2) is described under mild conditions, affording a single regioisomer of the sulfonyl fluorides. This method features broad functional group compatibility and delivers the target vinyl fluorosulfonimides in good to excellent yields. Moreover, gram-scale hydroamination of terminal and internal alkynes is achieved. Further transformations exploiting the reactivity of the vinyl fluorosulfonimide are subsequently developed for the synthesis of fluorosulfates and diphenyl sulfate.

(Hetero)Aryl Fluorosulfates (ArOSO2F): Good Coupling Partners in Transition‐metal‐catalyzed Reactions

“…Feng's group [72] recently developed a strategy to construct vinyl fluorosulfonimide frameworks via the hydroamination of alkynes with LiN(SO 2 F) 2 in the presence of Bu 4 NBF 4 . The compounds further reacted with phenol derivatives in THF at room temperature to produce aryl fluorosulfates (Scheme 10).…”

Synthesis ofN-alkenylisoquinolinonesviapalladium-catalyzed cyclization/C4–O bond cleavage of oxazolidines

“…4 As a result, a huge number of synthetic methods for the synthesis of enamides have been developed. The classical protocols include the addition of amides to alkynes, 5 the functionalization of ynamides, 6 the condensation of amides with carbonyl compounds, 7 the cross-coupling of amides with vinyl derivatives, 8 the Curtius rearrangement of α,β-unsaturated acyl azides, 9 and the elimination of hemiaminals or β-hydroxy-α-silylamides 10 (Scheme 1A). While these reactions can be very effective for constructing enamides, they still have some obvious limitations, including the utilization of excess oxidants, the exclusion of moisture, and the requirement of a step-wise process.…”

Nickel-Catalyzed Direct Cross-Coupling of Aryl Fluorosulfates with Aryl Bromides

“…Among the various newly developed electrophilic coupling partners, aryl fluorosulfates have been demonstrated to be an attractive and inexpensive alternative to aryl halides and other aryl sulfonates . Normally, aryl fluorosulfates can be readily synthesized in high yields starting from the corresponding phenol and cheap sulfuryl fluoride, and they display remarkable stability toward hydrolysis. , Apart from their wide utilities in the fields of polymer chemistry and chemical biology, aryl fluorosulfates have also found broad applications in organic synthesis. For instance, aryl fluorosulfates have been proven to be versatile arylating reagents which are capable of undergoing a spectrum of organic transformations, such as deoxyfluorination, carbonylation, formylation, phosphinylation, amination, , and cyanation …”