124992-97-8

Upstream product

• 3112-85-4 methylphenylsulfonate 
• 100-39-0 benzyl bromide 
• 27846-25-9 1-phenyl-2-(phenylsulfonyl)ethane 
• 103-63-9 1-phenyl-2-bromoethane 
• 1067227-26-2 C₂₅H₂₄O₄S 
• 873-55-2 sodium benzenesulfonate 

Downstream Products

• 124993-02-8 2-benzyl-1,3-diphenylpropyl phenyl sulfone 
• 1593772-05-4 C₂₁H₁₉⁽²⁾HO₂S 
• 1593772-08-7 C₂₁H₁₉⁽²⁾HO₂S 
• 26652-46-0 potassium benzenesulfinate 
• 50485-27-3 2-benzyl-1,3-diphenyl-1-propene 
• 3412-44-0 (1E)-1,3-diphenylpropene 
• 93727-20-9 1,1-dibenzyl-1-propanol 

Relevant academic research and scientific papers

Development of Palladium-Catalyzed Decarboxylative Allylation of Electron-Deficient Sulfones and Identification of Unusual Side Products

The use of sulfones as electron-withdrawing groups in substrates for palladium-catalyzed decarboxylative allylation was explored. A previously published trifluoromethanesulfonyl-based substrate was highly reactive and selective under mild conditions, but the substrate scope was not readily expanded. Instead, 3,5-bis(trifluoromethyl)phenyl sulfones were employed, thereby simultaneously retaining most of the electron deficiency and providing facile synthetic access. Optimization of the catalytic conditions to maximize the product distribution to a synthetically useful level of the allylation product over the protonation side product proved extremely challenging, with inconsistent and irreproducible results afforded with Pd2(dba)3 as the palladium source. A variety of substrates were subjected to the optimized catalytic conditions of PdCp(1-cinnamyl) and Xantphos in tetrahydrofuran at 50 °C for 30 min. These conditions were applicable to all substrates with the exception of the α,α-dimethyl allyl ester, which required more forcing conditions and afforded four products: the allylation and protonation products, as expected, along with a cyclopropylation product and an unprecedented pseudodimeric product. The mechanism for the formation of these unusual side products is considered.

Divergent reactivity of alkyl aryl sulfones with bases: Selective functionalization of ortho-aryl and α-alkyl units enabled by a unique carbanion transmetalation

The electron-accepting sulfonyl group exhibits a strong acidifying influence on neighboring α-H atoms. The Julia and related olefinations are based on this effect. Here a surprising reversal in the metalation selectivity of branched alkyl aryl sulfones is described. Such sulfones were found to initially undergo directed ortho-metalation with good regioselectivity, despite having a more acidic α-H atom. The structure of the alkyl unit profoundly, but predictably, influences the regioselectivity of the attack of the base. In β- and γ-branched ortho-(alkylsulfonyl)aryllithiums a transmetalation to the α-carbanion proceeds only upon warming. Correspondingly generated ortho- or α-carbanions were then selectively applied thus permitting access to synthetically interesting compound classes. An unusual lithiation selectivity and subsequent transfer of the metal upon warming was observed for various branched alkyl phenyl sulfones. This divergent reactivity was used to prepare substituted aryl sulfones as well as olefins by application of the Julia reaction. Copyright

Divergent Reactivity of Alkyl Aryl Sulfones with Bases: Selective Functionalization of ortho-Aryl and α-Alkyl Units Enabled by a Unique Carbanion Transmetalation

The electron-accepting sulfonyl group exhibits a strong acidifying influence on neighboring α-H atoms. The Julia and related olefinations are based on this effect. Here a surprising reversal in the metalation selectivity of branched alkyl aryl sulfones is described. Such sulfones were found to initially undergo directed ortho-metalation with good regioselectivity, despite having a more acidic α-H atom. The structure of the alkyl unit profoundly, but predictably, influences the regioselectivity of the attack of the base. In β- and γ-branched ortho-(alkylsulfonyl)aryllithiums a transmetalation to the α-carbanion proceeds only upon warming. Correspondingly generated ortho- or α-carbanions were then selectively applied thus permitting access to synthetically interesting compound classes.

Decarboxylative allylation using sulfones as surrogates of alkanes

(Chemical Equation Presented) α-Sulfonyl functional groups are traceless activating groups that facilitate catalytic decarboxylative allylations in high yield yet can be cleaved to allow the synthesis of simple allylated alkanes. Substrate studies suggest

Alkene synthesis: Elimination of arenesulfinic acid from alkyl aryl sulfones using potassium trimethylsilanolate as base

The use of potassium trimethylsilanolate as base to induce elimination of potassium arenesulfinate from alkyl aryl sulfones to produce E-alkenes is described. The reaction was appropriate for substrates containing a benzyl or allyl group α to the sulfone

Preparation of alcohols from sulfones and trialkylboranes

The reaction of sulfone anions with trialkylboranes followed by thermal isomerization of the obtained boron compounds in the presence of excess borane-methyl sulfide complex and by alkaline hydroperoxide oxidation yields primary alcohols.