Sulfones as Chemical Chameleons: Versatile Synthetic Equivalents of Small‐Molecule Synthons

Abstract

Sulfones are flexible functional groups that can act as nucleophiles, electrophiles, or even radicals. Changing the reaction conditions can completelya lter the reactivity of as ulfonyl group, and as ar esult, molecules bearing multiple sulfones are versatile building blocks. This Review highlights the unique ability of 1,1-and 1,2-bis(sulfones) to masquerade as av ast array of reactive synthons includingm ethane polyanions, vinyl cations,a nd all-carbond ipoles that would be difficultori mpossible to access directly.Scheme1.Selectedsyntheses and reactions of sulfones.Scheme2.Seminaluse of abis(sulfone) as am ethanedianion equivalent.[a] Prof. 11195 MinireviewScheme5.Pd-catalyzed allylic alkylation reactionsw ith bis(sulfones) as methylanion equivalents.Scheme6.Mitsunobumethylationfacilitated by ab is(sulfone) nucleophile.Scheme7.Formal methyl conjugate additiont oa,b-unsaturated aldehydes.Scheme8.Formal methyl conjugate additiont oa na,b-unsaturated ketone.Scheme11. Organocatalytic asymmetric allylic alkylation of Morita-Baylis-Hillmanc arbonates with FBSM.Scheme12. Formal asymmetric fluoromethylationofa ldimines.Scheme13. Formal asymmetric fluoromethylationofa ldehydes.Scheme14. Formal fluoromethylconjugate additionst oenals.Scheme15. Formal fluoromethylconjugate addition to enones.Scheme16. Alkylation of FBSM with alcohols and alkyl halides.Scheme17. Differential reactivity of BDT in difficult alkylation reactions.Scheme18. Annulative Mitsunobu reactionswith bis(sulfone) nucleophiles.Scheme19. Macrocyclizationr eactionsf acilitated by bis(sulfones). Scheme20. Syntheses of insect pheromones facilitated by bis(sulfones).Scheme21. To talsynthesis of (À)-trans-lauthisan.Scheme22. To talsyntheses of constanolactones Aand B.Scheme56. Usingabis(sulfone) to access an ambiphilic carbonyl synthon.Scheme57. Usingabis(sulfone) to access ac arbonyl diradical synthon.Scheme58. Syntheses of (AE)-21-noribogamineand (AE)-ibogamine facilitated by using abis(sulfone) as areplacement for lowmolecular weight olefins.

A Copper(I)‐Catalyzed Sulfonylative Hiyama Cross‐Coupling

“…3 Yet, the resulting sulfones are known to have a prominent biological activity as well as an important synthetic utility, making sulfonylative couplings particularly attractive. 4,5 From all commonly used organometallic reagents, organosilanes are presumably among the most appealing ones. In addition to being readily available, air-stable and relatively non-toxic, they display an improved functional-group tolerance compared to organolithium or -magnesium, thanks to their low nucleophilicity.…”

The Renaissance of Alkali Metabisulfites as SO2 Surrogates

“…4 Besides their use in the medicinal field, sulfone containing compounds display a wide range of reactivity in the field of synthetic organic chemistry and the moiety can act as a leaving group; therefore, it has been designated as a "chemical chameleon" by Trost. 5 Figure 1. Representative active sulfones containing molecules.…”

An efficient approach for the synthesis of novel methyl sulfones in acetic acid medium and evaluation of antimicrobial activity

“…Very recently, an ecofriendly approach to the construction of aryl methyl sulfone from SO 2 and methyl reagents is exemplified by Jiang et al [38]. An excellent review on sulfones was presented very recently by Trost et al [39]. In view of this and as an extension to our search for novel antimicrobial agents [40][41][42][43][44], the authors herein made an attempt to synthesize the titled sulfones and screen their antimicrobial properties.…”