A new property of geminal bishydroperoxides: Hydrolysis with the removal of hydroperoxide groups to form a ketone

Terent’ev, Alexander O.; Krivykh, O. B.; Krylov, Igor B.; Ogibin, Yu. N.; Nikishin, G. I.

doi:10.1134/s1070363210080165

Cited by 4 publications

(6 citation statements)

References 32 publications

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“…In that work, the bis hydroperoxyacetals derived from bulky alicyclic or strained cyclic frameworks underwent hydrolysis more rapidly than those based upon a strain-free backbone. 10 Our results demonstrate that these trends extend to bisperoxyacetals, with 2a undergoing complete hydrolysis under relatively mild conditions that fail to completely deprotect cyclohexanone-derived 4 . The lack of ring-expanded products observed during acid hydrolysis suggests that ionization of the acetal center is greatly favored relative to C-to-O migration (eq.…”

Section: Discussionmentioning

confidence: 60%

“…10 Investigations of conditions for alkylation of 1a are summarized in Table 1. There have been only a few reports describing alkylation of 1,1-dihydroperoxides.…”

mentioning

confidence: 99%

“…Compounds 1a and 1b were readily prepared via Re 2 O 7 -catalyzed condensation of the corresponding ketone with aqueous hydrogen peroxide (eq ) We chose to initially focus on the cyclododecanone-derived 1a on the basis of upon previous reports demonstrating that this DHP more readily undergoes acid hydrolysis compared with DHPs derived from strain-free ketones; it was our hope that this increased reactivity would extend to derived bisperoxyacetals . Investigations of conditions for alkylation of 1a are summarized in Table .…”

mentioning

confidence: 99%

“…Consistent with our hypothesis regarding the contribution of ring strain to peroxyacetal hydrolysis, bisperoxyacetal 4 could not be completely hydrolyzed under conditions that had proven effective for 2a (Table ).…”

mentioning

confidence: 99%

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Synthesis of Alkyl Hydroperoxides via Alkylation of gem-Dihydroperoxides

2013

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Section: Discussionmentioning

confidence: 60%

“…10 Investigations of conditions for alkylation of 1a are summarized in Table 1. There have been only a few reports describing alkylation of 1,1-dihydroperoxides.…”

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confidence: 99%

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Synthesis of Alkyl Hydroperoxides via Alkylation of gem-Dihydroperoxides

2013

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“…When performing the peroxidation of acetophenone 3 , we failed to achieve the complete conversion into geminal bishydroperoxide 4 because the reaction in an acidic aqueous medium is reversible . In the case of benzoylacetone 5 , the complete conversion was observed, but the reaction gave a complex mixture of products.…”

Section: Resultsmentioning

confidence: 99%

Selective Synthesis of Cyclic Peroxides from Triketones and H₂O₂

et al. 2012

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A method for the assembly of tricyclic structures containing the peroxide, monoperoxyacetal, and acetal moieties was developed based on the acid-catalyzed reaction of β,δ-triketones with H(2)O(2). Tricyclic compounds are formed selectively in yields from 39% to 90% by the reactions with the use of large amounts of strong acids, such as H(2)SO(4), HClO(4), or HBF(4), which act both as the catalyst and as the co-solvent. The reaction is unusual in that, despite the diversity of possible peroxidation pathways giving cyclic compounds and oligomers, the reaction proceeds with high selectivity and produces tricyclic peroxides via the monoperoxidation of the carbonyl groups in the β-positions and the transformation of the δ-carbonyl group into the acetal one. The syntheses are scaled up to tens of grams, and the resulting peroxides can be easily isolated from the reaction mixture.

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1,1‐Dihydroperoxides

Schwartz

Dussault

2014

Patai's Chemistry of Functional Groups

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Gem ‐dihydroperoxides ( g ‐DHPs), often referred to as 1,1‐dihydroperoxides, are a class of molecules of interest because of their reactivity as well as their utility as synthetic reagents and intermediates. This review begins with a listing of previous reviews and commercially available g ‐DHPs, followed by a brief discussion of safety and regulatory issues. The properties of g ‐DHPs are then overviewed, with an emphasis on the physical properties, biological activity, thermal stability, spectroscopic properties, and behavior on chromatographic media. The remaining sections describe the synthesis and reactions of g ‐DHPS. The largest of these sections describes the various methods for synthesis of g ‐DHPs based upon class of catalyst or reagent and compares applications of different reagents selected target skeletons. One of the most significant applications of g ‐DHPs, their use as precursors for 1,2,4,5‐tetraoxanes, is discussed in detail, including tabular comparisons of approaches to selected skeletons. The chapter concludes with a discussion of other important reactions of g ‐DHPs, including alkylations, nucleophilic and electrophile‐promoted additions to alkenes, acetalizations, acylations and acylation‐promoted fragmentations, acid‐promoted dimerizations and decompositions, silylations, and application as oxygen transfer agents.

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A new property of geminal bishydroperoxides: Hydrolysis with the removal of hydroperoxide groups to form a ketone

Cited by 4 publications

References 32 publications

Synthesis of Alkyl Hydroperoxides via Alkylation of gem-Dihydroperoxides

Synthesis of Alkyl Hydroperoxides via Alkylation of gem-Dihydroperoxides

Selective Synthesis of Cyclic Peroxides from Triketones and H₂O₂

1,1‐Dihydroperoxides

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A new property of geminal bishydroperoxides: Hydrolysis with the removal of hydroperoxide groups to form a ketone

Cited by 4 publications

References 32 publications

Synthesis of Alkyl Hydroperoxides via Alkylation of gem-Dihydroperoxides

Synthesis of Alkyl Hydroperoxides via Alkylation of gem-Dihydroperoxides

Selective Synthesis of Cyclic Peroxides from Triketones and H2O2

1,1‐Dihydroperoxides

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Selective Synthesis of Cyclic Peroxides from Triketones and H₂O₂