Synthesis of 1,1′-bishydroperoxydi(cycloalkyl) peroxides by homocoupling of 11–15-membered gem-bis(hydroperoxy)cycloalkanes in the presence of boron trifluoride

Terent’ev, Alexander O.; Kutkin, A. V.; Platonov, M.M.; Starikova, Z. A.; Ogibin, Yu. N.; Nikishin, G. I.

doi:10.1007/s11172-005-0383-4

Cited by 12 publications

(3 citation statements)

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“…The same derivatives were also prepared by ozonolysis of vinyl ethers in the presence of H 2 O 2 or by reaction of ketals with hydrogen peroxide in the presence of tungstic acid or in anhydrous ether under BF 3 catalysis . Condensation of bis-hydroperoxides leading to dihydroperoxydicycloalkyl peroxides and tetraoxadispiroalkanes ( VI ) or ozonides was also reported. − …”

Section: Introductionmentioning

confidence: 99%

Revising the Role of a Dioxirane as an Intermediate in the Uncatalyzed Hydroperoxidation of Cyclohexanone in Water

et al. 2015

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The mechanism of the oxidation of cyclohexanone with an aqueous solution of hydrogen peroxide has been investigated. Experiments revealed the preliminary formation of an intermediate, identified as cyclohexylidene dioxirane, in equilibrium with the ketone, followed by formation of 1-hydroperoxycyclohexanol (Criegee adduct). Computational analysis with explicit inclusion of up to two water molecules rationalized the formation of the dioxirane intermediate via addition of the hydroperoxide anion to the ketone and revealed that this species is not involved in the formation of the Criegee adduct. The direct addition of hydrogen peroxide to the ketone is predicted to be favored over hydrolysis of the dioxirane, the latter in competition with ring opening to carbonyl oxide followed by hydration. However, dioxirane may account for the formation of the bis-hydroperoxide derivative.

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Section: Introductionmentioning

confidence: 99%

Revising the Role of a Dioxirane as an Intermediate in the Uncatalyzed Hydroperoxidation of Cyclohexanone in Water

et al. 2015

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“…Our goal was to develop a convenient and selective single-step access to β-hydroperoxy-β-peroxylactones 6 via BF 3 -catalyzed cyclizations of a variety of acyclic precursors, β-ketoesters 1 and their silyl enol ethers 2 , alkyl enol ethers 3 , enol acetates 4 , cyclic acetals 5 , with H 2 O 2 (Scheme ). We have concentrated on the use of boron trifluoride as the peroxidation catalyst because this catalyst was shown to work well in a previous synthesis of bishydroperoxides, 1,1′-bishydroperoxydi(cycloalkyl) peroxides, and 1,2,4-trioxanes , as well as various peroxides from acetals and enol ethers …”

Section: Resultsmentioning

confidence: 99%

Five Roads That Converge at the Cyclic Peroxy-Criegee Intermediates: BF₃-Catalyzed Synthesis of β-Hydroperoxy-β-peroxylactones

et al. 2018

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We have discovered synthetic access to βhydroperoxy-β-peroxylactones via BF 3 -catalyzed cyclizations of a variety of acyclic precursors, β-ketoesters and their silyl enol ethers, alkyl enol ethers, enol acetates, and cyclic acetals, with H 2 O 2 . Strikingly, independent of the choice of starting material, these reactions converge at the same β-hydroperoxyβ-peroxylactone products, i.e., the peroxy analogues of the previously elusive cyclic Criegee intermediate of the Baeyer− Villiger reaction. Computed thermodynamic parameters for the formation of the β-hydroperoxy-β-peroxylactones from silyl enol ethers, enol acetates, and cyclic acetals confirm that the β-peroxylactones indeed correspond to a deep energy minimum that connects a variety of the interconverting oxygen-rich species at this combined potential energy surface. The target β-hydroperoxy-β-peroxylactones were synthesized from β-ketoesters, and their silyl enol ethers, alkyl enol ethers, enol acetates, and cyclic acetals were obtained in 30−96% yields. These reactions proceed under mild conditions and open synthetic access to a broad selection of β-hydroperoxy-βperoxylactones that are formed selectively even in those cases when alternative oxidation pathways can be expected. These βperoxylactones are stable and can be useful for further synthetic transformations.

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“…Modern approaches to the synthesis of organic peroxides are based upon the use of oxygen, ozone, and hydrogen peroxide as sources of the O-O group. The most common methods for the construction of the O-O group are the ene reaction of singlet oxygen with alkenes [50][51][52], [4 + 2], the cycloaddition of singlet oxygen to dienes [53,54], the peroxysilylation of alkenes by the Isayama-Mukayama reaction [55][56][57][58][59][60][61][62], the cyclization of unsaturated hydroperoxides by the Kobayashi reaction [63][64][65], processes with the participation of destabilized peroxycarbenium ions [66][67][68], the ozonolysis of alkenes [69][70][71][72][73][74], the nucleophilic addition of hydrogen peroxide to carbonyl compounds and their analogs catalyzed by acids [75][76][77][78][79][80][81][82][83][84][85][86][87][88][89][90][91], and the ring opening reaction of Donor-Acceptor cyclopropanes with alkyl hydroperoxides [92...…”

Section: Introductionmentioning

confidence: 99%

Lewis Acids and Heteropoly Acids in the Synthesis of Organic Peroxides

et al. 2022

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Organic peroxides are an important class of compounds for organic synthesis, pharmacological chemistry, materials science, and the polymer industry. Here, for the first time, we summarize the main achievements in the synthesis of organic peroxides by the action of Lewis acids and heteropoly acids. This review consists of three parts: (1) metal-based Lewis acids in the synthesis of organic peroxides; (2) the synthesis of organic peroxides promoted by non-metal-based Lewis acids; and (3) the application of heteropoly acids in the synthesis of organic peroxides. The information covered in this review will be useful for specialists in the field of organic synthesis, reactions and processes of oxygen-containing compounds, catalysis, pharmaceuticals, and materials engineering.

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Synthesis of 1,1′-bishydroperoxydi(cycloalkyl) peroxides by homocoupling of 11–15-membered gem-bis(hydroperoxy)cycloalkanes in the presence of boron trifluoride

Abstract: A procedure was developed for the synthesis of 1,1´ bishydroperoxydi(C 11 -C 15 cycloalkyl) peroxides based on homocoupling of geminal 11-15 membered bis(hydroperoxy)cycloalkanes in the presence of BF 3 •OEt 2 .

Cited by 12 publications

References 9 publications

Revising the Role of a Dioxirane as an Intermediate in the Uncatalyzed Hydroperoxidation of Cyclohexanone in Water

Revising the Role of a Dioxirane as an Intermediate in the Uncatalyzed Hydroperoxidation of Cyclohexanone in Water

Five Roads That Converge at the Cyclic Peroxy-Criegee Intermediates: BF₃-Catalyzed Synthesis of β-Hydroperoxy-β-peroxylactones

Lewis Acids and Heteropoly Acids in the Synthesis of Organic Peroxides

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Synthesis of 1,1′-bishydroperoxydi(cycloalkyl) peroxides by homocoupling of 11–15-membered gem-bis(hydroperoxy)cycloalkanes in the presence of boron trifluoride

Abstract: A procedure was developed for the synthesis of 1,1´ bishydroperoxydi(C 11 -C 15 cycloalkyl) peroxides based on homocoupling of geminal 11-15 membered bis(hydroperoxy)cycloalkanes in the presence of BF 3 •OEt 2 .

Cited by 12 publications

References 9 publications

Revising the Role of a Dioxirane as an Intermediate in the Uncatalyzed Hydroperoxidation of Cyclohexanone in Water

Revising the Role of a Dioxirane as an Intermediate in the Uncatalyzed Hydroperoxidation of Cyclohexanone in Water

Five Roads That Converge at the Cyclic Peroxy-Criegee Intermediates: BF3-Catalyzed Synthesis of β-Hydroperoxy-β-peroxylactones

Lewis Acids and Heteropoly Acids in the Synthesis of Organic Peroxides

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Product

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Five Roads That Converge at the Cyclic Peroxy-Criegee Intermediates: BF₃-Catalyzed Synthesis of β-Hydroperoxy-β-peroxylactones