A Protocol To Generate Phthaloyl Peroxide in Flow for the Hydroxylation of Arenes

Eliasen, Anders M.; Thedford, R. Paxton; Claussen, Karin R.; Yuan, Changxia; Siegel, Dionicio

doi:10.1021/ol501497y

Cited by 23 publications

(7 citation statements)

References 38 publications

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“…For example, Siegel and co-workers recently described the advantages of using a continuous flow system when phthaloyl peroxide was used as an oxidant. 36 Flow systems would ensure that the volumes remain small and all peroxides could be easily destroyed at the end of the reaction. Indeed, it is also worth pointing out that on an industrial scale, regardless of the solvent, there needs to be precautions taken when H 2 O 2 is used.…”

Section: Discussionmentioning

confidence: 99%

“…For example, Siegel and co-workers recently described the advantages of using a continuous flow system when phthaloyl peroxide was used as an oxidant. 36 Flow systems would ensure that the volumes remain small and all peroxides could be easily destroyed at the end of the reaction. (1 mol%, 0.0221 mmol), solvent (10 mL), 1-octene (0.25 g, 2.208 mmol), 27 °C.…”

Section: Discussionmentioning

confidence: 99%

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Cationic palladium(ii) complexes as catalysts for the oxidation of terminal olefins to methyl ketones using hydrogen peroxide

Cao

Bailie

et al. 2015

Green Chem.

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COMMUNICATIONThis journal is Ligated Pd(II) complexes have been studied for the catalytic oxidation of terminal olefins to their corresponding methyl ketones. The method uses aqueous hydrogen peroxide as the terminal oxidant; a sustainable and readily accessible oxidant. The choice of ligand, counterion and solvent all have a significant effect on catalytic performance and we were able to develop systems which perform well for these challenging oxidations.

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Section: Discussionmentioning

confidence: 99%

“…For example, Siegel and co-workers recently described the advantages of using a continuous flow system when phthaloyl peroxide was used as an oxidant. 36 Flow systems would ensure that the volumes remain small and all peroxides could be easily destroyed at the end of the reaction. (1 mol%, 0.0221 mmol), solvent (10 mL), 1-octene (0.25 g, 2.208 mmol), 27 °C.…”

Section: Discussionmentioning

confidence: 99%

Cationic palladium(ii) complexes as catalysts for the oxidation of terminal olefins to methyl ketones using hydrogen peroxide

Cao

Bailie

et al. 2015

Green Chem.

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“…The procedure has wide functional group tolerance, and arene overoxidation did not prove problematic. We believed two fundamental opportunities existed for development of this procedure: First, phthaloyl peroxide 1 is known to be very shock sensitive and explodes violently when heated, representing a significant hazard. , Second, the proposed reverse-rebound mechanism leading to 6 was based upon theoretical studies. Provision of experimental evidence to support this pathway would be of great importance to the understanding and development of this procedure.…”

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confidence: 99%

Arene Oxidation with Malonoyl Peroxides

et al. 2015

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Malonoyl peroxide 7, prepared in a single step from the commercially available diacid, is an effective reagent for the oxidation of aromatics. Reaction of an arene with peroxide 7 at room temperature leads to the corresponding protected phenol which can be unmasked by aminolysis. An ionic mechanism consistent with the experimental findings and supported by isotopic labeling, Hammett analysis, EPR investigations and reactivity profile studies is proposed.The oxidation and functionalization of hydrocarbons is a central facet of the chemical industry for the production of hightonnage commodities and the preparation of high-value pharmaceuticals, agrochemicals and fine chemicals. Therefore, methods for selective oxidation of C-H bonds are of great importance.1 Phenols represent a key class of oxidized hydrocarbon.2 While there are a small number of reports in which arenes are oxidized to the respective phenols using peroxides and strong acids as additives, 3 the oxidation of aromatic C-H bonds still presents a synthetic challenge specifically with respect to avoiding over oxidation. Scheme 1. C-H oxidation using phthaloyl peroxide. 2A recent report from the laboratories of Houk and Siegel described a metal-free oxidation of aromatic carbon-hydrogen bonds which was proposed to proceed through an intriguing reverse-rebound mechanism (Scheme 1). 4Reaction of mesitylene 2 with 1.3 equiv. of phthaloyl peroxide 1 in hexafluoroisopropanol (HFIP) followed by basic solvolysis gave the phenol 3 (97%). The method outlined in Scheme 1 represents a significant advance in arene oxidation. The proposed mechanistic pathway for the transformation suggested homolytic fission of the weak oxygen-oxygen bond leading to diradical 4. Addition of this radical to the arene gives 5 which though H-atom abstraction provides the observed product 6. Ester hydrolysis leads to the phenol 3 (97%, 2 steps). The procedure has wide functional group tolerance and arene over oxidation did not prove problematic. We believed two fundamental opportunities existed for development of this procedure: Firstly, phthaloyl peroxide 1 is known to be very shock sensitive and explodes violently when heated, representing a significant hazard. 5,6 Secondly, the proposed reverse-rebound mechanism leading to 6 was based upon theoretical studies. Provision of experimental evidence to support this pathway would be of great importance to the understanding and development of this procedure. In recent years we have been interested in the chemistry of cyclic diacylperoxides and have shown that malonoyl peroxide 7, 7 and related derivatives, 8 are effective for the syndihydroxylation of alkenes.9 This reagent provides significant advantages over phthaloyl peroxide 1 within the syndihydroxylation reaction in terms of yield, selectivity, reaction rate, substrate scope and operating temperature.10,11 Given our experience in understanding the mechanism of reactions involving the peroxide 7, 12 together with the specific advantages provided in alkene dihydroxylation we el...

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“…We now report that even better results can be achieved when phthaloyl peroxide 6 , easily accessible in one step from the commodity chemicals phthaloyl dichloride 7 and sodium percarbonate, is irradiated in the presence of azides. While thermolysis of phthaloyl peroxide 6 in the presence of arenes and alkenes has been reported to give hydroxylation and dihydroxylation products, respectively, via the dicarbonyl radical 8 , photolysis of 6 was found to lead to bisdecarboxylation with formation of benzyne, which underwent [2 + 2] and [2 + 4] cycloadditions with alkenes and 1,3-dienes, respectively (Scheme ). In the following, we report that one can also obtain [3 + 2] cycloadducts of benzyne in moderate to good yields when 6 is photolyzed in the presence of organic azides.…”

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confidence: 99%

[3 + 2] Cycloadditions of Azides with Arynes via Photolysis of Phthaloyl Peroxide Derivatives

2015

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A Protocol To Generate Phthaloyl Peroxide in Flow for the Hydroxylation of Arenes

Cited by 23 publications

References 38 publications

Cationic palladium(ii) complexes as catalysts for the oxidation of terminal olefins to methyl ketones using hydrogen peroxide

Cationic palladium(ii) complexes as catalysts for the oxidation of terminal olefins to methyl ketones using hydrogen peroxide

Arene Oxidation with Malonoyl Peroxides

[3 + 2] Cycloadditions of Azides with Arynes via Photolysis of Phthaloyl Peroxide Derivatives

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