With Vinyl sulfones

Treatment of a-lithionitriles with vinylic sulfones resulted in the formation of cyclized products, i.e., 3-oxothian-l, 1-dioxides 346 or cyclopropane derivatives 348. When a-lithiated aliphatic nitriles were used, carbanions 343, formed by the nucleophilic addition,... 

Scheme 14 Modification of proteasome threonine with vinyl sulfone ABPP probe...

Reaction of the Barton ester (124) with vinyl sulfone can be carried out under irradiation with a tungsten lamp (eq. 4.43) [123]. 

Michael addition is a facile reaction between nucleophiles and activated olefins and alkynes in which the nucleophile adds across a carbon-carbon multiple bond [25], For the preparation of hydrogels, the hydroxyl, thiol or amine functionalities have been reacted with vinyl sulfones [26-28], acrylates [29-31], acrylamides [32], and maleimides [33, 34] (Scheme 2). 

With vinyl sulfones as the substrates for the dihydroxylation procedure, a mixture of products results of which the a-hydroxy aldehyde is the major component (Scheme 3.8) [199]. 

Solid-supported 3-oxidopyridinium betaine (260) [295], generated by alkylation of 3-hydroxypyridine with bromo-Wang resin and then treating the resulting polymer-bound pyridinium bromide (259) with NaOCHs in propanol, was reacted with vinyl sulfone (Scheme 58). 

In contrast to acrylate, the solution-phase reaction with vinyl sulfone is known to proceed with high regio- and stereoselectivity [296, 297]. The solid-phase approach corroborated these results, leading to the 6-exo isomer (262) as the main isomer in good overall yield. Cleavage from the resin was performed with acid chlorides in acetonitrile in the presence of KI. 

Metz has developed a highly diastereoselective intramolecular Diels-Alder reaction of furans with vinyl sulfonates [22]. When hydroxyfuran 10 a was esterified with vinylsulfonic acid chloride, the intermediate sulfonate spontaneously underwent cycloaddition to give sultone 11a, Eq. 9. In the same manner, (-)-llb was obtained from (i )-10b which was derived from L-valine. 

Pyrrole-2-carboxylates. The ester enolate reacts with vinyl sulfones by way of conjugate addition and displacement. 

Mercaptan groups in keratin fibers also undergo nucleophilic addition reactions with active olefins (olefins containing a strong electron-withdrawing group attached to the double bond). Schoberl [91] has shown that reduced wool fiber reacts with vinyl sulfones. 

Truce, W. E., and V. V. Badiger Reaction of Dimethylsulfonium Methylide with Vinylic Sulfones. Formation of Aryl Cyclopropyl Sulfones. J. Org. Chem. 29, 3277 (1964). 

Figure 12.3 Peptide vinyl sulfones and peptide epoxyketones in activity-based proteasome profiling, (a) Catalytic mechanism of proteasome-mediated peptide bond cleavage, (b) Covalent adducts of protea-somes reacting with vinyl sulfones and...

On the other hand, Alexakis et al. have developed a sequential reaction exploiting the compatibility between a cationic iridium catalyst and chiral diphenylprolinol trimethylsilyl ether. The role of the iridium complex was proposed to isomerise the starting allylic primary alcohols into the corresponding aldehydes in the presence of H2, while the chiral amine catalyst promoted the a-functionalisation of these aldehydes through reaction with vinyl sulfone to give the corresponding Michael adducts as a mixture of syn-and (Z h -diastereomers obtained in moderate yields, moderate to excellent... 

Arylboronic acids engage in Heck reactions with vinyl sulfones and phosphonates to give the corresponding fi-arylated a,/3-unsaturated sulfones and phosphonates, respectively (eq... 

For example, Li synthesized poly (ethylene glycol) — poly(glutamic acid) block copolymer and the terminus of poly(ethylene glycol) was functionalized with vinyl sulfone groups for attaching monoclonal antibody targeting... 

Other cellulose ethers of related unsaturated nitriles have been prepared a-methyleneglutaronitrile, trans-crotonitrile, methacrylonitrile and fumaronitrile. Also, reversible reactions of alkali cellulose with acrylamide and reactions of alkali cellulose with vinyl sulfones have been reported. ... 

Kobayashi and coworkers developed a method for the facile introduction of a CF3 group using furan 210 as a dienophile [87]. Specifically, reaction of 210 with vinyl sulfone 211 produced 212 in 50% isolated yield (Scheme 13.50). Similarly, Zhu et al. reported the reaction... 

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