Working with organic peroxides in the academic lab

Dussault, Patrick H.

doi:10.13014/k2gt5kcj

Cited by 6 publications

(5 citation statements)

References 14 publications

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“…The tandem Hock rearrangement–Hosomi–Sakurai allylation was first investigated with indanyl hydroperoxide 1a in the presence of an acid catalyst and allyltrimethylsilane, to furnish 2-allylchromane 2a (Table ) [ Note that although the following organic peroxides were stable in our hands, it must be reminded that the manipulation of such reactive species must always be undertaken with great care ]. Decomposition was observed in the presence of BF 3 ·OEt 2 (2 equiv) at 0 °C (entry 1), while lowering the temperature at −78 °C afforded alkyl peroxide 3a with no sign of Hock rearrangement (entry 2).…”

Section: Results and Discussionmentioning

confidence: 99%

Tandem InCl₃-Promoted Hydroperoxide Rearrangements and Nucleophilic Additions: A Straightforward Entry to Benzoxacycles

et al. 2023

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The acid-catalyzed rearrangement of organic peroxides is generally associated with C−C-bond cleavages (Hock and Criegee rearrangements), with the concomitant formation of an oxocarbenium intermediate. This article describes the tandem process between a Hock or Criegee oxidative cleavage and a nucleophilic addition onto the oxocarbenium species (in particular a Hosomi−Sakurai-type allylation), under InCl 3 catalysis. It was applied to the synthesis of 2-substituted benzoxacycles (chromanes and benzoxepanes), including a synthesis of the 2-(aminomethyl)chromane part of sarizotan, and a total synthesis of erythrococcamide B.

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Section: Results and Discussionmentioning

confidence: 99%

Tandem InCl₃-Promoted Hydroperoxide Rearrangements and Nucleophilic Additions: A Straightforward Entry to Benzoxacycles

et al. 2023

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“…A solution of H 2 O 2 in Et 2 O (2.048 mol/L, ∼9.8% weight) was prepared by the extraction with Et 2 O (5 × 100 mL) from a 35% aqueous solution (100 mL) followed by drying over MgSO 4 . , A solution of H 2 O 2 in Et 2 O (90% weight) was prepared by evaporation of a 9.8% solution of H 2 O 2 in Et 2 O.…”

Section: Methodsmentioning

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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“…Additional references cited within the Supporting Information. [58][59][60][61][62][63][64][65][66][67][68][69][70][71][72][73][74][75] Deposition Number 2253685 (for 10 a) contains the supplementary crystallographic data for this paper. These data are provided free of charge by the joint Cambridge Crystallographic Data Centre and Fachinformationszentrum Karlsruhe Access Structures service.…”

Section: Associated Contentmentioning

confidence: 99%

Theoretical Investigation of the Mechanism of the Hock Rearrangement with InCl₃ as Catalyst**

et al. 2023

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The Hock rearrangement is an acid catalyzed reaction involving organic hydroperoxides and resulting in an oxidative cleavage of adjacent CÀ C bonds. It has significant industrial applications, like the production of phenol (cumene process), but it remains scarcely used in organic synthesis. In addition, its detailed mechanism has never been studied. Thus, we report herein a theoretical study of the Hock rearrangement, using InCl 3 as a Lewis acid catalyst. The aim of this work was to fully understand the mechanism of this fundamental reaction, and to rationalize the influence of the substrate electronic properties on the reaction outcome. Furthermore, the structure of the active indium(III) catalyst interacting with the peroxide substrate was investigated, revealing the co-existence of several energetically close reaction pathways. The coordinated monomeric form of the Lewis acid emerges as the most active catalyst compared to dimeric species. However, we show that In 2 Cl 6 species coordinated to the substrate are central in this catalytic cycle, primarily serving as a reservoir of active monomeric species.

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Working with organic peroxides in the academic lab

Cited by 6 publications

References 14 publications

Tandem InCl₃-Promoted Hydroperoxide Rearrangements and Nucleophilic Additions: A Straightforward Entry to Benzoxacycles

Tandem InCl₃-Promoted Hydroperoxide Rearrangements and Nucleophilic Additions: A Straightforward Entry to Benzoxacycles

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

Theoretical Investigation of the Mechanism of the Hock Rearrangement with InCl₃ as Catalyst**

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Working with organic peroxides in the academic lab

Cited by 6 publications

References 14 publications

Tandem InCl3-Promoted Hydroperoxide Rearrangements and Nucleophilic Additions: A Straightforward Entry to Benzoxacycles

Tandem InCl3-Promoted Hydroperoxide Rearrangements and Nucleophilic Additions: A Straightforward Entry to Benzoxacycles

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

Theoretical Investigation of the Mechanism of the Hock Rearrangement with InCl3 as Catalyst**

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Tandem InCl₃-Promoted Hydroperoxide Rearrangements and Nucleophilic Additions: A Straightforward Entry to Benzoxacycles

Tandem InCl₃-Promoted Hydroperoxide Rearrangements and Nucleophilic Additions: A Straightforward Entry to Benzoxacycles

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

Theoretical Investigation of the Mechanism of the Hock Rearrangement with InCl₃ as Catalyst**