Radical carbooxygenations of alkenes using hydroxamic acids

Quinn, Ryan K.; Schmidt, Valerie A.; Alexanian, Erik J.

doi:10.1039/c3sc51466h

Cited by 67 publications

(25 citation statements)

References 54 publications

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“…We next studied the scope of the alcohols (Table 4). Primary alcohols afforded the corresponding products 5a-5d in 87-91 %yields.Secondary alcohols delivered products 5e-5i in 59-85 %y ields.C innamyl alcohol and 3-phenyl-2propyn-1-ol afforded products 5j and 5k,b ut in lower [b] 1F e(OTf) 2 (5) THF 34 06 2 2F e(OTf) 2 (5) PhCH 3 34 05 4 3F e(OTf) 2 (5) dioxane 34 06 9 4F e(OTf) 2 (5) PhCF 3 34 04 3 5F e(OTf) 2 (5) CH 3 CN 34 05 6F e(OTf) 2 (5) DMA 34 0t race 7F e(OTf) 2 (5) DMF 34 0t race 8F e(OTf) 2 (5) CH 3 OH 34 0t race 9F e(OTf) 3 (5) dioxane 34 07 0 10 Fe(OTf) 3 (5) dioxane 35 07 2 11 Fe(OTf) 3 (5) dioxane 36 06 3 12 Fe ( [a] RCOOH was applied and alkyl diacyl peroxides or alkyl tert-butyl peresters were utilized after simple filtration.Conditions for Table 2a:1b (2.0 mmol), RCOOH (6.0 mmol), DCC (3.0 mmol), H 2 O 2 (3.0 mmol), DMAP (0.12 mmol), Fe(OTf) 3 (5 mol %), dioxane (8 mL). Conditions for Table 2b: 1b (1.5 mmol), RCOOH (6.0 mmol), DCC (4.5 mmol), TBHP (7.2 mmol), DMAP (0.12 mmol), Fe(OTf) 3 (5 mol %), dioxane (6 mL).…”

Section: Angewandte Chemiementioning

confidence: 99%

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Iron‐Catalyzed Decarboxylative Alkyl Etherification of Vinylarenes with Aliphatic Acids as the Alkyl Source

et al. 2017

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Because of the lack of effective alkylating reagents, alkyl etherification of olefins with general alkyl groups has not been previously reported. In this work, a variety of alkyl diacyl peroxides and peresters generated from aliphatic acids have been found to enable the first iron-catalyzed alkyl etherification of olefins with general alkyl groups. Primary, secondary and tertiary aliphatic acids are suitable for this reaction, delivering products with yields up to 97 %. Primary and secondary alcohols react well, affording products in up to 91 % yield.

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Section: Angewandte Chemiementioning

confidence: 99%

“…We initiated our studies by screening the solvents used in the alkyl etherification reaction of styrene with lauroyl peroxide (LPO) in presence of Fe(OTf) 2 ( Table 1, entries [1][2][3][4][5][6][7][8]. Dioxane was found to be the most efficient solvent for this reaction and afforded the product in 69 %yield.…”

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confidence: 99%

Iron‐Catalyzed Decarboxylative Alkyl Etherification of Vinylarenes with Aliphatic Acids as the Alkyl Source

et al. 2017

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“…Apart from alkenes containing nucleophiles, some alkenes with reactive functional groups that could generate radicals – such as alkenes with N‐arylhydroxamic acids, hydrazones,, and so on – have also been applied to intramolecular difunctionalization. Generally, the addition of radicals generated in situ from internal groups of alkenes to carbon–carbon double bonds triggers these reactions and forms new radical intermediates, which may trap radical acceptors to afford the difunctionalization products.…”

Section: Intramolecular Radical Difunctionalization Of Simple Alkenesmentioning

confidence: 99%

Recent Advances in Radical Difunctionalization of Simple Alkenes

2017

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Direct difunctionalization of simple alkenes, the incorporation of two functional groups onto a carbon–carbon double bond, is of particular interest to the chemical community owing to its important applications in organic synthesis. Mechanistically, two types of reactions – metal‐catalyzed nucleophilic difunctionalization and radical difunctionalization – dominate this research field. Radical difunctionalization is more appealing from a synthetic perspective than metal‐catalyzed nucleophilic difunctionalization because it allows the conversion of simple alkenes into complex molecules in a rapid and convenient manner. Furthermore, radical difunctionalization allows addition to simple alkenes by various carbon‐centered radicals and even heteroatom‐centered radicals. This review gives an overview of intermolecular and intramolecular radical difunctionalization of simple alkenes, with an emphasis on the reaction patterns and mechanisms, as well as potential applications in synthetic chemistry.

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“…Alternatively, Alexanian and co-workers demonstrated the radical-mediated oxyallylation of alkenes with allyl sulfones using hydroxamic acids as the radical precursor with the assistance of PhSO2NH2 (Scheme 1b). 28 Although highly practical, the types of oxygen-centered radicals remain limited. Encouraged by the works of Han, 29,30 Wang, 31 and our group 32 on the copper-catalyzed iminoxyl radical-mediated oxyfunctionalization of alkenes, we envisioned that iminoxyl radical may also be involved in the oxyallylation with allyl sulfones.…”

Section: Introductionmentioning

confidence: 99%