Alkene Syn Dihydroxylation with Malonoyl Peroxides

Griffith, James C.; Jones, Kevin M.; Picon, Sylvain; Rawling, Michael J.; Kariuki, Benson M.; Campbell, Matthew; Tomkinson, Nicholas C. O.

doi:10.1021/ja1066674

Cited by 116 publications

(65 citation statements)

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“…However at this time, a radical or a single-electron-transfer pathway also cannot be ruled out. [11] The occurrence of 21 and 22 is supported by the isolation of 7 and 8 by Siegel et al in a ratio of 1:2; [10] this is consistent with the faster formation of five-membered over eight-membered rings. Tomkinson et al isolated the sevenmembered lactone 23 analogous to 7, but the highly strained spiro compound 24 analogous to 8 was not observed.…”

mentioning

confidence: 52%

“…As a possible solution to this problem, Tomkinson et al investigated the use of malonyl peroxide derivatives for the dihydroxylation of alkenes. [11] Cyclopropylmalonyl peroxide (11) was found to be the most reactive peroxide in the series of three-, four-, and five-membered spirocyclic malonyl peroxides 11-13 for the dihydroxylation of styrene.…”

mentioning

confidence: 99%

“…[11] Nevertheless, because of the reactive nature of peroxides, special precaution must always be exercised in handling such compounds.…”

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confidence: 99%

“…[13] [b] Bond angles a derived from X-ray structure analysis. [11] Scheme 3. Comparison of the stereospecifity and reactivity of 5, 6, and 11 in the reactions of selected alkenes.…”

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confidence: 99%

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Metal or No Metal: That Is the Question!

Schwarz

Reiser

2011

Angew Chem Int Ed

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alkenes · dihydroxylation · organocatalysis · oxygen heterocycles · peroxides Theoxidativefunctionalizationofalkenesisamongthemost extensively investigated synthetic transformations in organic chemistry. Simple oxidative cleavage, [1a-d] halogenation, [1e] halohydrin formation, [1f] and Wacker oxidation [1g] are widely applied in academia and industry. Moreover, transitionmetal-catalyzed epoxidation, [2a-e] dihydroxylation, [2f-h, 3] and aminohydroxylation [2i,j] reactions, for which enantioselective variants with broad scope have been developed, serve as the cornerstone of many complex-molecule syntheses.A stunning example of the progress in organocatalytic oxidation is the development of the epoxidation of alkenes with dioxiranes. Early examples with simple dimethyldioxirane generated from acetone (1) and Oxone (potassium peroxymonosulfate) in situ were reported in 1979 by Edwards et al., [4a] and the scope of the reaction was expanded by Curci et al. in 1980.[4b] The same group developed the first asymmetric epoxidation in 1984 with dioxiranes derived from chiral ketones 2 and 3;[4c] however, only low asymmetric induction could be achieved at this time (Figure 1). Quite a number of other chiral ketones were subsequently investigated [4d,e] to improve the enantiomeric excess until in 1996 the readily available fructose-derived ketone 4 was introduced by Shi et al.[4f] While stoichiometric amounts of 4 were initially necessary to achieve high enantioselectivity, only one year later the same group was able to establish a catalytic variant by adjusting the pH of the reaction;[4g] under these conditions the reaction rivalled the efficiency of metalbased asymmetric epoxidations (Scheme 1).Another class of organic compounds, organic acyl peroxides, could potentially break the dominance of metalcatalyzed processes for the oxidative functionalization of alkenes. So far, the primary oxidant OsO 4 is still the reagent of choice for the syn dihydroxylation of alkenes [2f-h, 3] for both asymmetric and non-asymmetric metal-catalyzed reactions.

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confidence: 99%

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Metal or No Metal: That Is the Question!

Schwarz

Reiser

2011

Angew Chem Int Ed

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“…All solvents were distilled before use using standard procedures. Ethyl 4-acetyl-5-oxohexanoate (1a) [126], 3-benzylpentane-2,4-dione (1b) [127], 3-(4-chlorobenzyl)pentane-2,4-dione (1c) [128], 3-acetylheptane-2,6-dione (1f) [129], ethyl 2-acetylhexanoate (1h) [130], ethyl 2-acetyl-4-cyanobutanoate (1i) [131], ethyl 2-benzyl-3-oxobutanoate (1j) [132] and diethylmalonyl peroxide (2a) [20] were synthesized according to the literature.…”

Section: General Materials and Methodsmentioning

confidence: 99%

Silica gel mediated oxidative C–O coupling of β-dicarbonyl compounds with malonyl peroxides in solvent-free conditions

Bityukov

Vil

Merkulova

et al. 2017

Pure and Applied Chemistry

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For the first time silica gel was observed to activate peroxides in oxidative coupling reactions. Here we report silica gel mediated oxidative C-O coupling of β-dicarbonyl compounds with cyclic diacyl peroxides affording α-acyloxy derivatives with 100 % atom efficiency. The highest yields of coupling products were achieved in solvent free conditions. C-O coupling products were prepared in yields up to 86 %.

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5,6-Dioxaspiro[2.4]heptane-4,7-dione

Tomkinson

2016

Encyclopedia of Reagents for Organic Synthesis

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Alkene Syn Dihydroxylation with Malonoyl Peroxides

Cited by 116 publications

References 20 publications

Metal or No Metal: That Is the Question!

Metal or No Metal: That Is the Question!

Silica gel mediated oxidative C–O coupling of β-dicarbonyl compounds with malonyl peroxides in solvent-free conditions

5,6-Dioxaspiro[2.4]heptane-4,7-dione

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