CuBr-Mediated Oxyalkylation of Vinylarenes under Aerobic Conditions via Cleavage of sp<sup>3</sup> C−H Bonds α to Oxygen

Cheng, Kai; Huang, Lehao; Zhang, Yuhong

doi:10.1021/ol900947d

Cited by 135 publications

(64 citation statements)

References 70 publications

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“…[12] This radical could be further oxidized to a cation, [13] whereas DTBP could react with transition-metal salts and further undergoes homolytic cleavage to afford a tert-butoxyl radical and high-valent metal hydroxide. [12] This radical could be further oxidized to a cation, [13] whereas DTBP could react with transition-metal salts and further undergoes homolytic cleavage to afford a tert-butoxyl radical and high-valent metal hydroxide.…”

Section: Methodsmentioning

confidence: 99%

Direct Functionalization of Tetrahydrofuran and 1,4‐Dioxane: Nickel‐Catalyzed Oxidative C(sp³)H Arylation

Liu

et al. 2013

Angew Chem Int Ed

278

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CHoose nickel: The nickel‐catalyzed oxidative arylation of C(sp3)H bonds has been achieved. Several substituted arylboronic acids and various C(sp3)H bonds were found to be suitable substrates for this novel transformation, which is likely to proceed through a radical pathway. This method allows the introduction of simple ether derivatives to construct α‐arylated ethers. FG=functional group.

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Section: Methodsmentioning

confidence: 99%

Direct Functionalization of Tetrahydrofuran and 1,4‐Dioxane: Nickel‐Catalyzed Oxidative C(sp³)H Arylation

Liu

et al. 2013

Angew Chem Int Ed

278

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“…With a-keto radicals and alkenes,ananalogous sequence provides g-tert-butylperoxyl ketones as products. [56] Theselective crosscoupling of peroxyl radicals with Cradicals was also used as ak ey step in related syntheses of alcohols, [57] ethers, [58] and nitroalkanes. [59] Furthermore,m ore complex cascades were developed along those lines.…”

Section: Alkyl Peroxidesmentioning

confidence: 99%

The Persistent Radical Effect in Organic Synthesis

2019

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Radical–radical couplings are mostly nearly diffusion‐controlled processes. Therefore, the selective cross‐coupling of two different radicals is challenging and not a synthetically valuable transformation. However, if the radicals have different lifetimes and if they are generated at equal rates, cross‐coupling will become the dominant process. This high cross‐selectivity is based on a kinetic phenomenon called the persistent radical effect (PRE). In this Review, an explanation of the PRE supported by simulations of simple model systems is provided. Radical stabilities are discussed within the context of their lifetimes, and various examples of PRE‐mediated radical–radical couplings in synthesis are summarized. It is shown that the PRE is not restricted to the coupling of a persistent with a transient radical. If one coupling partner is longer‐lived than the other transient radical, the PRE operates and high cross‐selectivity is achieved. This important point expands the scope of PRE‐mediated radical chemistry. The Review is divided into two parts, namely 1) the coupling of persistent or longer‐lived organic radicals and 2) “radical–metal crossover reactions”; here, metal‐centered radical species and more generally longer‐lived transition‐metal complexes that are able to react with radicals are discussed—a field that has flourished recently.

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“…1140 This tandem process is comprised of a hydroxyalkylation of an alkene followed by further oxidation to the ketone. A plausible mechanism for this reaction is outlined in Scheme 626.…”

Section: Reactions Of Ethersmentioning

confidence: 99%

Aerobic Copper-Catalyzed Organic Reactions

et al. 2013

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24 peroxide [Cu I (pyr)(tpb)] 10 mol % TBHP, 1 atm O 2 , 1:2 AcOH/pyr, rt, 24 h ∼2.5 26 74 g 35 25 n-hexane aldehyde CuCl 2 , 18-crown-6 1 atm O 2 , MeCHO, CH 2 Cl 2 , 70 °C, 24 h 2.4 91 h 9 34a 26 n-decane aldehyde Cu II Cl 16 Pc-AM(PS) 3 equiv of PhCHO, MeCN, 1 atm O 2 , 50 °C 15.4 100 i 61 a See Chart 2 for ligand structures. b Also 28% cyclohexene. c Also 26% cyclohexene. d Mixture of alcohol and hydroperoxide. e Remainder of product is cyclohexene. f Approximately 93:7 of 1-adamantol/2-adamantol. g Approximately 98:2 of 1-adamantol/2-adamantol. h Afforded oxidation products in an approximately 1:1 ratio at the 2-and 3-positions. i Mixture of decanones.

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CuBr-Mediated Oxyalkylation of Vinylarenes under Aerobic Conditions via Cleavage of sp³ C−H Bonds α to Oxygen

Cited by 135 publications

References 70 publications

Direct Functionalization of Tetrahydrofuran and 1,4‐Dioxane: Nickel‐Catalyzed Oxidative C(sp³)H Arylation

Direct Functionalization of Tetrahydrofuran and 1,4‐Dioxane: Nickel‐Catalyzed Oxidative C(sp³)H Arylation

The Persistent Radical Effect in Organic Synthesis

Aerobic Copper-Catalyzed Organic Reactions

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CuBr-Mediated Oxyalkylation of Vinylarenes under Aerobic Conditions via Cleavage of sp3 C−H Bonds α to Oxygen

Cited by 135 publications

References 70 publications

Direct Functionalization of Tetrahydrofuran and 1,4‐Dioxane: Nickel‐Catalyzed Oxidative C(sp3)H Arylation

Direct Functionalization of Tetrahydrofuran and 1,4‐Dioxane: Nickel‐Catalyzed Oxidative C(sp3)H Arylation

The Persistent Radical Effect in Organic Synthesis

Aerobic Copper-Catalyzed Organic Reactions

Contact Info

Product

Resources

About

CuBr-Mediated Oxyalkylation of Vinylarenes under Aerobic Conditions via Cleavage of sp³ C−H Bonds α to Oxygen

Direct Functionalization of Tetrahydrofuran and 1,4‐Dioxane: Nickel‐Catalyzed Oxidative C(sp³)H Arylation

Direct Functionalization of Tetrahydrofuran and 1,4‐Dioxane: Nickel‐Catalyzed Oxidative C(sp³)H Arylation