Evidence for a perepoxide intermediate in the 1,2-cycloaddition of singlet oxygen to adamantylideneadamantane: nucleophilic oxygen atom transfer to sulfoxides

Schaap, A. Paul; Recher, S. G.; Faler, Gary R.; Villaseñor, Steven R.

doi:10.1021/ja00344a067

Cited by 59 publications

(11 citation statements)

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“…Intermolecular trapping of PE intermediate in the 1 O 2 ene reaction with simple alkenes has fascinated researchers for many years. Interestingly, pinacolone, 41 sulfoxides, 42 phosphites, 43 sulfenate and sulfinate esters 44 phite have also been used to trap intermediates in reactions of 1 O 2 with diethyl sulfide 45 and trans-cyclooctane, 46 respectively. Despite these interesting findings, Tonachini and co-workers, based on theoretical studies, found that the trimethyl phosphite mediated abstraction of the terminal oxygen atom from a PE and an open-chain intermediate (such as intermediate 8 or 9) affords the same epoxide product.…”

Section: Introductionmentioning

confidence: 99%

Recent Mechanistic Insights in the Singlet Oxygen Ene Reaction

Alberti¹,

Orfanopoulos²

2010

Synlett

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Singlet oxygen reacts with alkenes, which bear allylic hydrogens, in an ene fashion to afford allylic hydroperoxides. This reaction, apart from its synthetic usefulness, has received extensive mechanistic attention. Numerous experimental studies (e.g., trapping of intermediates, deuterium kinetic isotope effects, regio-or stereoselectivity studies etc.) and to a lesser extend computational work, support a stepwise mechanism with the formation of a threemembered ring (perepoxide-like) intermediate. This Account mainly highlights our group's earlier and recent experimental efforts to ascertain facts relating to this concept.

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Section: Introductionmentioning

confidence: 99%

Recent Mechanistic Insights in the Singlet Oxygen Ene Reaction

Alberti¹,

Orfanopoulos²

2010

Synlett

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“…This result has provoked controversy [2] concerning the origin of the epoxide which is thought to arise from the perepoxide 4 or the zwitterionic peroxide 5, the presumed precursor to the dioxetane. In certain instances when electrophilic agents are present, such as aryl sulfoxides, 4 or 5 can be intercepted and reduced to epoxide 3 [3]. However, we have deduced that dioxetane 2 is the bonafide product of the reaction of 1 with singlet oxygen, whereas epoxide 3 is the consequence of an incidental, parasitic reaction involving radicals.…”

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confidence: 76%

The Reaction of Singlet Oxygen with Adamantylideneadamantane Mediated by Rose Bengal

Jefford

Jiménez-Estrada

Barchietto

et al. 1990

Helvetica Chimica Acta

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The photo-oxygenation of adamantylideneadamantane (1) on siliceous supports using admixed granules of ion-exchange resin fixed to methylene blue (MB) and rose bengal (RB) gave exclusively the corresponding dioxetane derivative 2 for the former sensitizer, while the latter gave 2 and traces of the epoxide 3. RB and the charge-transfer complex produced from N-ethylcarbazole and 2,4,5,6-tetranitrofluoren-9-one both reacted with chemically generated singlet oxygen to give superoxide radical anion. Trapping of the latter with 5,5-dimethyl-Ipyrroline 1-oxide gave an adduct exhibiting a characteristic ESR spectrum. The treatment of 1 in MeOH with 30% aqueous H202 for 22 h at 60" gave 3 in 100% yield. Repetition of this experiment in the presence of 2,6-di(rertbuty1)-p-cresol caused no significant change. These results indicate that singlet oxygen reacts with 1, in the presence of RB, by two different processes. The first leads to dioxetane formation. The second process involves conversion of singlet oxygen by RB to superoxide radical anion which subsequently gives H202 so producing epoxide 3 from 1.

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“…Trapping of the intermediate with sulphoxides 24 , phosphites 25 and sulphenates or sulphinate esters 26 in the photooxygenation of adamantylidenoadamantane, and theoretical calculations 27 -31 as well, support the perepoxide as the most possible intermediate. Many authors consider an intermediate exciplex 32 -34 instead of the polar perepoxide.…”

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confidence: 81%

Selective Formation of Allylic HydroperoxidesviaSinglet OxygeneneReaction

Orfanopoulos

Vougioukalakis

Stratakis

2009

Patai's Chemistry of Functional Groups

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Introduction Regioselective Formation of Allylic Hydroperoxides Diastereoselective Formation of Allylic Hydroperoxides Selective Formation of Allylic Hydroperoxides by Dye‐Sensitized Intrazeolite Photooxygenation Synthetic Applications Perspectives Acknowledgements

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Evidence for a perepoxide intermediate in the 1,2-cycloaddition of singlet oxygen to adamantylideneadamantane: nucleophilic oxygen atom transfer to sulfoxides

Cited by 59 publications

References 1 publication

Recent Mechanistic Insights in the Singlet Oxygen Ene Reaction

Recent Mechanistic Insights in the Singlet Oxygen Ene Reaction

The Reaction of Singlet Oxygen with Adamantylideneadamantane Mediated by Rose Bengal

Selective Formation of Allylic HydroperoxidesviaSinglet OxygeneneReaction

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