111171-95-0Relevant academic research and scientific papers
Electroinitiated Oxygenation of Alkenyl Sulfides and Alkynes in the Presence of Thiophenol
Yoshida, Jun-ichi,Nakatani, Shogo,Isoe, Sachihiko
, p. 4855 - 4865 (2007/10/02)
Electrolysis of alkenyl sulfides in the presence of thiophenol with bubbling of molecular oxygen gave the corresponding α-(phenylthio) carbonyl compounds with the consumption of a catalytic amount of electricity.An electroinitiated radical chain mechanism has been proposed.The reaction also took place without electrochemical initiation, but much (5-50 times) longer reaction time was required for the completion of the reaction.The potential utility of the present reaction in organic synthesis is demonstrated by the net 1,2-transposition of a phenylthio group and a carbonyl group.The electroinitiated oxygenation of ketene dithioacetals also proceeded smoothly to give the corresponding α-(phenylthio) thiol esters.It was also found that the electroinitiated oxygenation of alkynes in the presence of thiophenol gave α-(phenylthio) carbonyl compounds.A mechanism involving the initial formation of alkenyl sulfides has been proposed.
Intramolecular Aromatic Substitution with Bisthiocarbocations. Variations of Lewis Acid, Solvent and Orthothio Substituents
Gamage, Swarna A.,Smith, Robin A. J.
, p. 815 - 824 (2007/10/02)
The effects of Lewis acid, solvent and orthothio substituent have been examined with regard to intramolecular electrophilic aromatic substitution (annulation) with bisthiocarbocations.A suspension of silver trifluoromethanesulfonate in dichloromethane, creating bis(arylthio)carbocations, was found to be the most effective for annulation of six-membered rings.
Synthesis and Reactivity of Lithiated γ-Functionalised Ketene Dithioacetals. Generation of a Flexible β-Lithioacrylate Equivalent
Dziadulewicz, Edward,Hodgson, David,Gallagher, Timothy
, p. 3367 - 3374 (2007/10/02)
The synthesis of 1,1,3-tris(phenylthio)prop-1-ene (8) is described.Anion (9), obtained by deprotonation of (8) with lithium di-isopropylamide, reacts with a wide range of electrophiles to give the γ-substituted adducts (10) exclusively.The relative importance of steric and electronic effects in determining the high γ-regioselectivity observed for (9) have been evaluated using a series of related ketene dithioacetals (12)-(15), and (17).The equivalence of anion (9) to a β-lithioacrylate has been illustrated by constructing a series of α,β-unsaturated γ- and δ-lactones and a short synthesis of (+/-)-eldanolide is also described.Anion (9) undergoes a facile dimerisation in the presence of oxygen to give dimer (20) and a mechanistic rationale for this observation is presented.
