Oxidative cleavage of 2-substituted cycloalkane-1,3-diones and of cyclic β-ketoesters by copper perchlorate / oxygen

Cossy, Janine; Belotti, D.; Bellosta, Véronique; Brocca, Daniela

doi:10.1016/0040-4039(94)88083-2

Cited by 48 publications

(26 citation statements)

References 11 publications

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“…Oxidative cleavage of the copper enolate results in the formation of α-diketoacids in good to excellent yields (Scheme 285). 567 The lower-yielding reactions are caused by oxidative degradation of starting material or product. The reaction substrate must be symmetrical; if different enolate isomers can form the reaction will give a complex mixture of products.…”

Section: Reactions Of Carbonyls and Carbonyl Equivalentsmentioning

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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Section: Reactions Of Carbonyls and Carbonyl Equivalentsmentioning

confidence: 99%

Aerobic Copper-Catalyzed Organic Reactions

et al. 2013

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“…7 While the products reported were achiral and unfunctionalized, the transformation is striking for its simplicity and use of cheap, unmodified catalysts. To the best of our knowledge, this reaction has not been employed in asymmetric synthesis.…”

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confidence: 99%

“…With an ambident electrophile such as 2-cyclohexen-1-one, methyl acetoacetate undergoes (3+3)-annulation 18 providing bicyclo[3.3.1]nonanone 10 (Scheme 4). Oxidative deacylation of (±)- 10 led to a ring cleavage reaction 7a that yielded cyclohexanol 11 as a single isomer (87% yield) with all four oxygenated functional groups differentiated. Notably, the product is the synthetic equivalent of two challenging reactions: enone conjugate glyoxylation and diastereoselective ketone acetate aldolization.…”

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confidence: 99%

Asymmetric Synthesis of α-Keto Esters via Cu(II)-Catalyzed Aerobic Deacylation of Acetoacetate Alkylation Products: An Unusually Simple Synthetic Equivalent to the Glyoxylate Anion Synthon

Steward

Johnson

2011

Org. Lett.

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A simple and efficient method for the preparation of β-stereogenic α-keto esters is described using a copper(II)-catalyzed aerobic deacylation of substituted acetoacetate esters. The substrates for the title process arise from catalytic, enantioselective conjugate additions and alkylation reactions of acetoacetate esters. The mild conditions do not induce racemization of the incipient enolizable α-keto ester. The reaction is tolerant of esters, certain ketones, ketals, and nitro groups and utilizes inexpensive, readily available materials.

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“…The metal ion is necessary for the one-electron oxidation of the dicarbonyl compound 1a. The probability of the one-electron oxidation of 1,3-dicarbonyl compounds with MnA C H T U N G T R E N N U N G (OAc) 3 , [124][125][126][127][128] FeA C H T U N G T R E N N U N G (ClO 4 ) 3 , [131,132] (NH 4 ) 2 CeA C H T U N G T R E N N U N G (NO 3 ) 6 , [133,134] and CuA C H T U N G T R E N N U N G (ClO 4 ) 2 [135] is supported by the published data. The generation of iminoxyl radicals A under the conditions similar to the reaction conditions was confirmed by ESR spectroscopy.…”

Section: Resultsmentioning

confidence: 99%

Iminoxyl Radical‐Based Strategy for Intermolecular CO Bond Formation: Cross‐Dehydrogenative Coupling of 1,3‐Dicarbonyl Compounds with Oximes

et al. 2014

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Cross-dehydrogenative C À O coupling of 1,3-diketones and 1,3-keto esters with oximes was realized for the first time. The reaction proceeds in the presence of the oxidants [KMnO 4 , /KMnO 4 ] system; yields are 27-92%. The synthesis can be easily scaled up to gram quantities of the target products. Appa-rently, the reaction proceeds via a radical mechanism in which the oxidizing agent serves to generate radicals from oximes and perform the one-electron oxidation of 1,3-dicarbonyl compounds. The formation of oxime radicals was confirmed quantitatively by electron spin resonance (ESR) spectroscopy. The coupling described in the present study is the first example of the selective intermolecular reaction involving unstable iminoxyl radicals generated in situ. Scheme 1. Cross-dehydrogenative C À O coupling of 1,3-dicarbonyl compounds 1a-l with oximes 2a-i.

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Oxidative cleavage of 2-substituted cycloalkane-1,3-diones and of cyclic β-ketoesters by copper perchlorate / oxygen

Cited by 48 publications

References 11 publications

Aerobic Copper-Catalyzed Organic Reactions

Aerobic Copper-Catalyzed Organic Reactions

Asymmetric Synthesis of α-Keto Esters via Cu(II)-Catalyzed Aerobic Deacylation of Acetoacetate Alkylation Products: An Unusually Simple Synthetic Equivalent to the Glyoxylate Anion Synthon

Iminoxyl Radical‐Based Strategy for Intermolecular CO Bond Formation: Cross‐Dehydrogenative Coupling of 1,3‐Dicarbonyl Compounds with Oximes

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