Diels-Alder Reactions with Arylethenesulfonyl Fluorides

N‐Heterocyclic Carbene Catalyzed Synthesis of δ‐Sultones via α,β‐Unsaturated Sulfonyl Azolium Intermediates

“…The chemistry of unsaturated sulfonyl(V) fluorides (e.g., 3 ) was first studied in 1954 by Truce and Hoerger who reported the Diels–Alder reaction of 2‐ para ‐nitrophenylethylene sulfonyl fluoride ( 3 a , R= p ‐NO 2 C 6 H 4 ) with cyclopentadiene 7. Twenty‐five years later, Krutak, Hyatt, and co‐workers thoroughly investigated the use of ethylene sulfonyl fluoride (ESF, 3 b , R=H) as a Michael acceptor 8.…”

[3+2] Cycloaddition of an Azomethyne Ylide and Vinyl Sulfonyl Fluorides ― an Approach to Pyrrolidine‐3‐sulfonyl Fluorides

“…Notably, the reaction could be scaled up to 25 g without any significant change in the outcome. Encouraged by this result, we prepared a series of -arylsubstituted vinyl sulfonyl fluorides 1b-1j using a variation of the previously reported method, [45,28] i.e., chlorosulfonation of the corresponding styrenes 5b-5h with varied electronic and steric properties (42-71 % yield), followed by reaction of the sulfonyl chlorides 6b-6h with KHF 2 (92-99 % yield, Scheme 3). In addition, bicyclic α, -unsaturated sulfonyl fluorides 1i-1k were also prepared in 26-60 % overall yield using the same reaction sequence.…”

“…General Remarks: Solvents were purified according to standard procedures . Sulfonyl halides 1 , , and 6 , were obtained using reported procedures. All other starting materials were purchased from commercial sources.…”

“…Moreover, the parent vinyl sulfonyl fluoride ( 1a ) was referred to as “the most perfect Michael acceptor ever found” , . To date, [3+2] cycloaddition reactions with nitrones, as well as Diels–Alder reactions, of 1 have been reported in the literature. In this paper, we describe reactions of 1 with nonstabilized azomethine ylide 2 , as well as some further transformations of the resulting products 3 (Scheme ).…”

Synthesis of novel 1,2,4-thiadiazinane 1,1-dioxidesviathree component SuFEx type reaction

“…[20][21][22] There are only four publications that, so far, have reported the use of a,b-unsaturated sulfonyl uoride based compounds as starting materials in organic synthesis. [23][24][25][26] Based on our earlier experience with the reactivity of aryl a,b-unsaturated sulfonyl uoride towards various amine nucleophiles 17 (Scheme 1), we hypothesized that an a,b-unsaturated sulfonyl uoride of type 4 can possibly be explored for the synthesis of thiadiazinanes. This hypothesis was based on observation of low amounts of the six-membered product was formed along with the major b-sultam product 5 when p-nitrophenylethenesulfonyl uoride was subjected to excess methyl amine in methylene chloride as a solvent and triethylamine as additional base at room temperature (Scheme 1).…”