58749-54-5Relevant academic research and scientific papers
Allylation with Pummerer-generated Subtituted Vinylthionium Ions
Hunter, Roger,Michael, Joseph P.,Simon, Clive D.,Walter, Daryl S.
, p. 9365 - 9376 (1994)
Pummerer-derived substituted vinylthionium ions (allyl phenyl sulfoxide, TMSOTf, EtN(i-Pr)2, CH2Cl2, -78 deg C) with a β-trimethylsilylmethyl (2), γ-phenyl (14), or γ-phenylthio (15) group allylate the enol silyl ethers of acetophenone (3) and cyclohexanone (4) in good yield.Allylation with (14) and (15) required slow addition of base in order to limit the rate of production of intermediate, and thus avoid unwanted sila-Pummerer type products.Huenigs's base conjugate addition was not observed in these cases.Both the (E)- and (Z)- forms of allyl sulfoxide (15) were shown to equilibrate to the (E)-transoid conformer prior to allylation resulting in exclusive (E)-vinyl sulfide formation.Blocking of the γ-position resulted in preferential α-attack.
Effect of chalcogenyl substituent on the course of allyl rearrangement at chalcogenation of 1,3-dichloropropene
Levanova,Nikonova,Grabel’nykh,Russavskaya,Albanov,Rozentsveig,Korchevin
, p. 615 - 623 (2016/07/06)
Formation of 1,3-dichalcogenylpropene at the treatment of 1,3-dichloropropene with organic dichalcogenides in a redox system hydrazine hydrate–KOH is governed by the possibility of an allyl rearrangement. In the presence of bases this rearrangement proceeds via carbanion partially stabilized by the chalcogenyl substituent. The effectivity of the stabilization and consequently the probability of the rearrangement varies in the series of substituents PhS > BnS > PhSe. In the stage of the direct nucleophilic substitution of chlorine the anion PhSe?possesses the highest activity.
