67229-92-9

Upstream product

• 82480-46-4 C₂₂H₂₀O₄S₂ 
• 28010-12-0 5-phenylpenta-2,4-dienoic acid 
• 873-55-2 sodium benzenesulfonate 
• 5535-48-8 PVS 
• 4363-35-3 Dihydroxy-styryl-boran 
• 38066-16-9 diethyl [(phenylthio)methyl]phosphonate 
• 70960-88-2 trimethyl ((1E,3E)-4-phenylbuta-1,3-dien-1-yl)silane 
• 14371-10-9 (E)-3-phenylpropenal 
• 56069-39-7 diethyl phenylsulfonylmethylphosphonate 

Downstream Products

• 1245924-56-4 1-(2-[(E,2R,3R)-5-phenyl-3-((phenylsulfonyl)methyl)pent-4-en-2-yl](S)-phenylsulfinyl)-4-methylbenzene 

Relevant academic research and scientific papers

PhI(OAc)2 mediated decarboxylative sulfonylation of β-aryl-α,β-unsaturated carboxylic acids: A synthesis of (E)-vinyl sulfones

A highly efficient metal-free decarboxylative sulfonylation protocol for the preparation of (E)-vinyl sulfones from of β-aryl-α,β-unsaturated carboxylic acids using sodium sulfinates and (diacetoxyiodo)benzene (PhI(OAc)2) was developed. This strategy offers a simple and expedient synthesis of (E)-vinyl sulfones bearing a wide variety of functional groups. A radical-based pathway has been proposed for this decarboxylative sulfonylation reaction.

Convenient synthesis of α,β-unsaturated sulfones via a Mizoroki-Heck reaction of arylboronic acids with phenyl vinyl sulfones

Palladium acetate catalyzed Mizoroki-Heck reaction of arylboronic acids with phenyl vinyl sulfones afford α,β-unsaturated sulfones in good yields.

Remarkably Facile Hexatriene Electrocyclizations as a Route to Functionalized Cyclohexenones via Ring Expansion of Cyclobutenones

This Communication describes a cascade reaction sequence that leads to highly functionalized cyclohexenones starting from reaction of cyclobutenones with α-lithio-α,β-unsaturated sulfones and amides. The hexatriene-cyclohexadiene cyclization steps presumed to be involved in these transformations are among the most facile hexatriene electrocyclizations reported thus far. Copyright

Palladium-catalyzed cascade reaction of α,β-unsaturated sulfones with aryl iodides

Unlike traditionally used acyclic 1,2-disubstituted alkenes, the reaction of α,β-unsaturated phenyl sulfones with aryl iodides under Heck reaction conditions (Pd(OAc)2 as catalyst, Ag2-CO3 as base in DMF at 120°C) takes place mainly by a cascade process, involving one unit of the alkene and three units of the aryl iodide, to afford a substituted 9-phenylsulfonyl-9,10-dihydrophenanthrene, The dominant formation of this 3:1 coupling product, instead of the Heck trisubstituted olefin, shows that aromatic C-H activation processes can compete with the usually fast syn β-hydrogen elimination step in the Heck arylation of an acyclic olefin. The structural scope of this palladium-catalyzed cascade arylation of α,β-unsaturated sulfones has proved to be wide with regard to substitution at the β-position (alkyl, aryl, or alkenyl substitution), substitution at the sulfone unit (alkyl or phenyl sulfones), and configuration at the C=C bond (trans or cis). Moreover, although less favored than in the case of the arylation of α,β-unsaturated sulfones, similarly substituted 9,10-dihydrophenanthrenes have also been obtained in the case of α,β-unsaturated phosphine oxides and α,β-unsaturated phosphonate esters. A Pd0-pdII-pdIV mechanistic pathway involving the successive formation of highly electrophilic σ-alkylpalladium intermediates and palladacycles is proposed for this multi-component arylation.

First synthesis, X-ray structure analysis and reactions of alkenyltriphenylbismuthonium salts

Treatment of triphenylbismuth difluoride with alkenyltrimethylsilanes 1 or trimethylsilyl cyanidealkenyltrialkylstannanes 3 in the presence of boron trifluoride-diethyl ether gave the corresponding alkenyltriphenylbismuthonium tetrafluoroborates 2 in moderate to good yields. An X-ray crystallographic analysis of the salt 2e confirmed the distorted tetrahedral geometry of the central bismuth atom. When treated with a sulfinate 5 or the thiolate 11, the salts 2 readily transferred both the vinyl and phenyl moieties to these nucleophiles to afford the sulfones 7-10 or the sulfides 12, 13, respectively. In the presence of a palladium catalyst, the salt 2e underwent the Heck-type reaction with ethyl acrylate 17 to afford the dienoate 18 and cinnamate 19 in moderate yields. Action of KOBut on the salt 2b yielded p-tolylacetylene 22, while a similar reaction with the salt 2e in the presence of the styrenes 23 gave the cyclopropanes 24. A Hammett study of the latter reaction has suggested a possible involvement of an alkylidenecarbene as the intermediate in these base-promoted reactions.

Elimination and Addition Reactions. Part 41. Nucleophilic Eliminative Fission of Cyclopropanes: the Coiled Spring Effect of Ring Strain on Nucleofugality and its Evaluation

Rates have been measured of sulphonyl-activated eliminative ring fissions of a series of six cyclopropanes in which the leaving group is stabilised by alkoxycarbonyl, cyano, or sulphonyl groups.The measurements allow assignment of ranks (nucleofugalities) to carbon leaving groups in systems in which the connection to the leaving group is strained by incorporation in a cyclopropane ring.The values obtained are compered with those obtained for a unstrained (acyclic) analogues.Rank enhancements of about 9(log) units are obtained; these enhancements suggests that free energies of activation for leaving-group expulsion are reduced by about 53 kJmol-1, or about 46 percent of these excess of enthalpy of the strained ring, notwithstanding the small degree of ring fission in the transition structure.The effect of phenyl substitution at the leaving group suggests that cleavage of the ring is very little advanced in the transition structure, although this is variable with the nature of the leaving-group stabilisation.This is the first direct determination of the effect of strain on nucleofugality.

Synthesis of α,β-γ,δ-unsaturated sulfones and sulfoxides via the Horner-Emmons reaction

α,β-γ,δ-Unsaturated sulfones and sulfoxides have been prepared via the Horner-Emmons reaction of α,β-unsaturated carbonyl compounds with α-phosphoryl sulfones and sulfoxides.