116279-69-7Relevant 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 (2007/10/02)
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.
[3+3] Annulation by sequential two electron and one electron allylation
Ward, Dale E.,Kaller, Brian F.
, p. 843 - 846 (2007/10/02)
3-phenylthio-2-(trimethylsilymethyl)propene is a convenient conjunctive reagent for the preparation of methylenecyclohexanes via a [3+3] annulation. The trimethylsilyl group facilitates the Lewis acid catalyzed allylation of an aldehyde or acetal while the phenylthio group directs a 6-endo-trig radical cyclization reaction.
THE CERIUM (III) MEDIATED REACTION OF TRIMETHYLSILYLMETHYL MAGNESIUM CHLORIDE WITH ESTERS AND LACTONES: THE EFFICIENT SYNTHESIS OF SOME FUNCTIONALISED ALLYLSILANES OF USE IN ANNULATION REACTIONS
Lee, Thomas V.,Channon, Julia A.,Cregg, Carmel,Porter, John R.,Roden, Frances S.,Yeoh, Helena T-L.
, p. 5877 - 5886 (2007/10/02)
The use of cerium (III) chloride alters the chemoselectivity of the reaction of trimethylsilylmethyl magnesium chloride with ester-acetals and also greatly improves the efficiency of reaction with lactones.In addition it gives improved preparations of the useful intermediates (7), (13), (18), (20) and (22) and gives direct access to the valuable functionalised allylsilanes (1) to (3) of use in annulation reactions.
THE SCOPE OF A NEW MASKED MICHAEL REACTION INVOLVING A PUMMERER INTERMEDIATE
Hunter, Roger,Simon, Clive D.
, p. 2257 - 2260 (2007/10/02)
Huenig's base has been found to compete as a nucleophile in the alkylation of Pummerer generated vinylthionium ions.This discovery has been used in extending the scope of the novel masked Michael addition reaction.
