68969-27-7

Upstream product

• 36525-02-7 <(E)-3,3-dimethyl-1-butenyl>mercuric chloride 
• 98-09-9 benzenesulfonyl chloride 
• 163977-73-9 3,3-Dimethylbut-1-en-1-yl phenyl sulfide 
• 38238-75-4 (E)-2-chloroethenyl phenyl sulfone 
• 37530-86-2 1-phenylsulfonyl-2-(phenylthio)ethene 
• 52244-26-5 cis-β-Bromovinyl phenyl sulfone 
• 20408-25-7 trans-β-Bromovinyl phenyl sulfone 
• 58202-75-8 trans β-iodovinyl phenyl sulfone 
• 56069-39-7 diethyl phenylsulfonylmethylphosphonate 
• 630-19-3 pivalaldehyde 
• 26620-11-1 (E)-2-chlorovinylthiobenzene 
• 35088-66-5 2-bromoethyl phenyl sulfide 
• 38442-51-2 tert-butylmercury chloride 
• 88486-41-3 1-(tri-n-butylstannyl)-2-(phenylsulfonyl)ethene 

Relevant academic research and scientific papers

Stereoselective Synthesis of Z-α,β-Unsaturated Sulfones Using Peterson Reagents

New Peterson reagents were prepared by introducing alkyloxy groups on the silicon atom in order to fix the conformation of the sulfone anion. The reagents 1d and 1e reacted with a variety of aldehydes after the treatment with Li-base to give Z-α,β-unsaturated sulfones with up to >99:1 selectivity in good to excellent yields. For the reaction with aliphatic aldehydes, CPME (cyclopentyl methyl ether) is the choice of solvent, while DME (1,2-dimethoxyethane) gave higher selectivity for the reaction with aromatic aldehydes.

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

Efficient dehydrocyanation of hindered 1-substituted olefins

The chlorosulfides 7 which formed quantitatively by reaction of olefins 5 with PhSCl under neutral conditions could be converted into the unsaturated nitriles 6 in good yields by sequential treatment with alkaline cyanides and MCPBA, a similar result being observed by reversing this order.

A method for the conversion of sulfoximines to sulfones: Application to polymer-bound sulfoximines and to the synthesis of chiral sulfones

Reaction of N-alkyl, N-aryl, and N-H sulfoximines with m- chloroperbenzoic acid cleanly gives the corresponding sulfones in high yield. In the case of the cleavage of N-alkyl and N-arylsulfoximines, formation of the corresponding nitroso compounds as the other reaction product was proven. Starting from enantio- and diastereopure sulfoximines, a number of chiral sulfones, including the axially chiral sulfone 6 and the sulfonyl- functionalized homoallylic alcohol 8, have been prepared. Reaction of the enantiopure sulfoximine 30 with Merrifield resin gave the polymer-bound sulfoximine 32. Oxidative cleavage of 32 afforded the sulfone 16 in high yield. Deprotonation of the sulfoximine resin 32 and reaction of Li-32 with benzaldehyde and propanal furnished the β-hydroxysulfoximine resins 33a and 33b, respectively. Oxidative cleavage of 33a and 33b readily afforded the β- hydroxy sulfones 14a and 14b, respectively.

A useful method for configuration assignement of vinyl sulfides; stereochemical reassessment of the radical addition of benzenethiol to alkynes

A comparative analysis of the 1H NMR spectra of (E)- and (Z)-phenyl and alkyl sulfides and their corresponding sulfones provides a useful method for establishing their configuration.Although by employing this method we generally confirm our previous configurational assignement for benzenethiol/alkyne adducts, those for (E)- and (Z)-3-(phenylsulfanyl)hex-3-ene and 4-phenylsulfanyl)oct-4-ene, are shown to have been assigned incorrectly.In the light of the present results it is concluded that radical addition of benzenethio to alkynes at 100 deg C generally proceeds with trans-selectivity.This conclusion is the reverse of our earlier claim for the effect that benzenethiol adds to terminal alkynes and alkylphenylacetylenes in a trans-stereoselective mode, but in a cis-stereoselective mode to dialkylacetylenes bearing (rather) bulky alkyl groups.

IODINE ATOM TRANSFER ADDITION REACTIONS WITH ALKYNES. PART 1: ALKYL IODIDES

Simple 2*- and 3*- alkyl iodides add smoothly to electron deficient alkynes under standard atom transfer conditions (10percent Bu3SnSnBu3), sunlamp photolysis).Mechanistic experiments help to interpret stereochemical and yield trends, and a new model for

Electron-transfer processes. 43. Attack of alkyl radicals upon 1-alkenyl and 1-alkynyl derivatives of tin and mercury

Alkyl radicals, obtained by reaction of Bu3Sn? or ClHg? with alkylmercury halides, will undergo regioselective and in some cases stereospecific substitution by a free radical chain addition-elimination mechanism with 1-alkenylstannanes or -mercurials. The chain reaction is also observed for 1-alkynyl derivatives and in the photostimulated demercuration of mixed alkyl and 1-alkenyl- or 1-alkynylmercurials. Chain propagation with alkyl radical formation is also observed to occur in the reactions of β-eliminated ClHg? with Grignard reagents in PhH-THF solution. In competitive reactions of Bu3Sn? or ClHg? with pairs of alkylmercury chlorides, it is observed that a tert-butylmercurial is >1000 times more reactive than a n-butylmercurial, suggesting a concerted dissociate electron-transfer process not involving the intermediacy of RHg? species.

Reactions of Alkylmercurials with Heteroatom-Centered Acceptor Radicals

The relative reactivities of alkylmercury halides toward PhS., PhSe., or I. decrease drastically from R = tert-butyl to R = sec-alkyl to R = n-butyl, indicative that R. is formed in the rate-determining step in the attack of these radicals upon RHgCl.The alkyl radicals thus formed will enter into chain reactions in which a heteroatom-centered radical (A.) is regenerated from substrates such as RS-SR, ArSe-SeAr, ArTe-TeAr, PhSe-SO2Ar, Cl-SO2Ph; ZCH=CHA (A = Cl, I, SPh, SO2Ph); or PhCCHA (A = I, SPh, SO2Ph). β-Styrenyl (PhCH=CHA, Ph2C=CHA) and β-phenethynyl (PhCCA) systems with A = I, Br, SO2Ph also enter into chain reactions with mercury(II) salts with the ligands PhS, PhSe, PhSO2, or (EtO)2PO.The relative reactivities of a series of reagents toward t-Bu. and of PhCH=CHA, Ph2C=CHA, and PhCCA toward c-C6H11. are reported as well as the regioselectivity of t-Bu. attack observed for 1,2-disubstituted ethylenes (ZCH=CHA) with Z and A from the group Ph, Cl, Br, I, SO2Ph, SPh, Bu3Sn.Reactions of (E)- and (Z)-PhCH=CHI or MeO2CCH=CHI with t-Bu. or c-C6H11. occurred in a regioselective and stereospecific (retention) manner.Reactions of (E)- and (Z)-ClCH=CHCl occurred in a nonstereospecific manner in which the E/Z product ratio increased with the bulk of the attacking radical.A similar effect on the E/Z product ratios was observed for (Z)-MeO2CCH=CHCl.