123207-76-1

Upstream product

• 91925-45-0 1,4-diphenyl-2,3-dioxabicyclo<2.2.2>oct-5-ene 
• 21113-62-2 1,4-diphenyl-1,3-cyclohexadiene 
• 91925-45-0 1,4-diphenyl-2,3-dioxabicyclo[2.2.2]oct-5-ene 

Relevant academic research and scientific papers

Iron(II)-promoted rearrangement of 1,4-diaryl-2,3-dioxabicyclo[2.2.2]oct-5-enes: A mechanism distinct from that postulated previously

Reactions of 1,4-diaryl-2,3-dioxabicyclo[2.2.2]oct-5-enes 1a-c (1a: Ar=p-FC6H4, 1b: Ar=C6H5, 1c: Ar=p-MeC6H4) with FeBr2 afforded syn-1,2;3,4-bis(epoxy)-1,4-diarylcyclohexanes 4a-c and cis-3,6-diaryl-2,3-epoxycyclohexanones 5a-c as major products instead of the previously reported 1-aroyl-3-aryl-2,3-epoxycyclopentanes 2a-c.

Electron-transfer Photochemistry of Endoperoxides

Derivatives of 1,2-dioxacyclohex-4-ene and 2,3-dioxabicyclooct-5-ene (endoperoxides, EPs) form EDA complexes with tetracyanoethylene (TCNE).The phenyl-substituted EPs 3a, 4a, 4b and 6 undergo electron-transfer-induced reactions when the EDA complexes are irradiated.Two types of reactions are observed depending on the ring system.Monocyclic EPs (3a, 4a and 4b) afford furan derivatives, possibly through the Criegee-type rearrangement, and dehydration, whereas the bicyclic EP 6 undergoes cycloreversion through the C-O bond cleavage.

Ruthenium(II)-Catalyzed Reactions of 1,4-Epiperoxides

The behavior of 1,4-epiperoxides in the presence of transition-metal complexes is highly dependent on the structures of the substrates and the nature of the metal catalysts.Reaction of saturated epiperoxides such as 1,3-epiperoxycyclopentane, 1,4-epiperoxycyclohexane, or dihydroascaridole catalyzed by RuCl2(PPh3)3 in dichloromethane gives a mixture of products arising from fragmentation, rearrangement, reduction, disproportionation, etc.Prostaglandin H2 methyl ester undergoes clean and stereospecific fragmentation to afford methyl(5Z,8E,10E,12S)-12-hydroxy-5,8,10-heptadecatrienoate and malonaldehyde.Bicyclic 2,3-didehydro 1,4-epiperoxides give the syn-1,2:3,4-diepoxides by the same catalyst.The monocyclic analogues are transformed to a mixture of diepoxides and furan products.The stereochemical outcome of the epoxide formation reflects unique differences in the ground-state geometry of the starting epiperoxide substrates.FeCl2(PPh3)2 serves as a useful catalyst for the skeletal change of sterically hindered bicyclic 2,3-didehydro 1,4-epiperoxides to the syn-diepoxides.In addition, the Fe complex best effects the conversion of 1,4-unsubstituted 2,3-didehydro epiperoxides to furans.The Ru-catalyzed reactions are interpreted in terms of the intermediacy of inner-sphere radicals formed by atom transfer of the Ru(II) species to peroxy substrates, in contrast to the Fe-catalyzed reactions proceeding via free, outer-sphere radicals generated by an electron-transfer mechanism.