79069-18-4Relevant academic research and scientific papers
Reaction Manifolds of Alkenes with benzene: Stereospecific syn-1,2-Ditosyloxylation of the Carbon-Carbon Double Bond and Other Processes
Rebrovic, Louis,Koser, Gerald F.
, p. 2462 - 2472 (2007/10/02)
The treatment of various alkenes with benzene (1) in CH2Cl2 gives moderate yields of the corresponding vic-bis(tosyloxy)alkanes (2).When cis- and trans-2-butenes, cis- and trans-2-pentenes, cis-3-hexene, cis-4-octene, and cyclohexene are reactants, the tosyloxy ligands are introduced with syn stereospecifity.With cis- and trans-stilbenes, however, a mixture of meso- and dl-1,2-diphenyl-1,2-bis(tosyloxy)ethanes results from either alkene.Some alkenes react with 1 in a different way.Thus, trans-3-hexene and trans-4-octene with 1 give low yields of 2,5-bis(tosyloxy)-3-hexene and 3,6-bis(tosyloxy)-4-octene, respectively.Evidence is presented that the formation of the bis(tosyloxy)alkenes proceeds via initial oxidation of the trans alkenes by 1 to conjugated dienes and subsequent conjugate ditosyloxylation of the dienes.In a few cases, molecular rearrangements occur.Thus, norbornene with 1 gives 2,7-bis(tosyloxy)norbornane, among other products, while 1,1-diphenylethylene gives deoxybenzoin (major product) and (β,β-diphenylethenyl)phenyliodonium tosylate.The reaction of styrene with 1 depends on the medium; when CH2Cl2 is present, the product is 1-phenyl-1,2-bis(tosyloxy)ethane, but in the absence of solvent, the product is 1,1-bis(tosyloxy)-2-phenylethane.Most alkenes react with 1 to give p-toluenesulfonic acid as a byproduct, and, in rare instances, (iodoxy)benzene is obtained.A mechanism for the vic-ditosyloxylation of alkenes by 1, consistent with the observed syn stereospecificity, is proposed.
Functionalization of Alkenes and Alkynes with benzene. Bis(tosyloxy)alkanes, Vinylaryliodonium Tosylates, and Alkynylaryliodonium Tosylates
Koser, Gerald F.,Rebrovic, Louis,Wettach, Richard H.
, p. 4324 - 4326 (2007/10/02)
benzene (1) reacts with various alkenes to give bis(tosyloxy)alkanes and with various alkynes to give either vinylaryliodoniumtosylates or alkynylaryliodonium tosylates.In the presence of 1, 1,1-diphenylethylene undergoes oxidative rearrangement and phenyliodination.
