Use of Ruthenium Tetroxide as a Multi-purpose Oxidant

Berkowitz, Lewis M.; Rylander, Paul N.

doi:10.1021/ja01557a053

Cited by 233 publications

(73 citation statements)

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“…Since the introduction in 1953 of ruthenium tetraoxide as an organic oxidant [1], this reagent has been widely used [2] to oxidise alkenes [3,4],alkynes [4c], alcohols [3, 4e, 5], diols or sugars [6], ketones [bb, 7], acyclic or cyclic ethers (thioethers) [4b, 8], amines…”

Section: Introductionmentioning

confidence: 99%

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RuO4-mediated oxidation ofN-benzylated tertiary amines. Are amineN-oxides and iminium cations reaction intermediates?

Petride¹,

Drăghici²,

Florea³

et al. 2004

Open Chemistry

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N-Benzylmorpholine, -piperidine, and -pyrrolidine (1A-C, resp.) are oxidised by RuO4 (generated m situ) at both endocyclic and exocyclic (benzylic) N-c~ methylene positions to afford lactams (and dioxo-derivatives) and benzaldehyde (and benzoyl derivatives), respectively. The N-oxides of 1A-C, formed by a minor side reaction, are not involved as intermediates. Control experiments showed the transient formation of endo-and exocyclic iminium cations trapped with NaCN as the corresponding nitriles. The proposed course of the RuO4-mediated oxidation of 1A-C involves the consecutive steps 1 a iminium cations + cyclic enamine ~ oxidation products. The endocyclic/exocyclic regioselectivity of the oxidation reaction lies between 0.8 (for 1A) and 2.1 (for 1B). The amine cation radical and the N-c~-C. carbon centered radical seem not to be involved. 9 Central European Science Journals. All rights reserved.

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Section: Introductionmentioning

confidence: 99%

“…Control experiments [g], [t~] rA ( 10C (28) A 2C (7.5), 4C (1.5), 8C (20.5), 3C (1), 9 (25.5) [3] unk ( 6A [d] 7A [d] …”

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confidence: 99%

RuO4-mediated oxidation ofN-benzylated tertiary amines. Are amineN-oxides and iminium cations reaction intermediates?

Petride¹,

Drăghici²,

Florea³

et al. 2004

Open Chemistry

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“…This is consistent with the observation of a relatively narrow multiplet for H-11 in 6b and a much broader multiplet for H-12 in 7. However, as it was desirable to have more conclusive evidence for the nature of the cyclic ether functions in these compounds, we decided to attempt the oxidation of the ethers to the corresponding lactones using ruthenium tetroxide (21,22). Thus, a catalytic quantity of a solution of RuO, in carbon tetrachloride was added to the impure ether (7), isolated from the hypoiodite reaction of la, in the same solvent and the resulting mixture was stirred vigorously at room temperature with excess of an aqueous solution of sodium periodate.…”

Section: Resultsmentioning

confidence: 99%

Ring C Functionalized Diterpenoids. Part I. The Hypoiodite Reaction as a Route to Ring C Functionalized Kauranes and Phyllocladanes

McAlees¹,

McCrindle²

1973

Can. J. Chem.

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16p-ent-17-Kauranol ( l a ) , the corresponding C-19 ester ( l b ) , and 168,17-phyllocladanol (2), on reaction with lead tetraacetate -iodine in refluxing cyclohexane, suffered intramolecular attack mainly at C-11. Thus l a gave as major products the 11-en-17-01 (3a) and the 11!3-iodo-l2!3,17-ether (4a), along with minor amounts of the 9,ll-en-128,17-ether (5), the 11!3,17-ether (6a), and, resulting from attack at C-12, the 12!3,17-ether (7). The phyllocladanol 2 gave the 11 p,17-ether (8) and the 9,ll-en-1213,17-ether (9). The assignment of structures 6a, 7 , and 8 to the ethers rests on their conversion with ruthenium tetroxide into the corresponding lactones, 10, 11, and 12.L'ent-l6p Kauranol-17 ( l a ) , l'ester C-19 correspondant (16) et le phyllocladanol-16p,17 (2), subissent une attaque intramoleculaire principalement au site C-l l lorsqu'ils sont reflues dans le cyclohexane en prtsence de tCtraacCtate de plomb-iode. Ainsi, l a a donnt, comme produits majeurs, I'ene-11 01-17 (30) et I'ether-12p,17 iodo-llp (4a), en meme temps que des petites quantites d'ither-12p,17 ene-9,11 (5), d'tther-llp,l7 (6a) ainsi que d'ether-12p,17 ( 7 ) resultant de I'attaque en C-12. Le phyllocladanol 2 a conduit a l'ether-118,17 ( 8 ) et a l'tther-12!3,37 ene-9,l I (9). L'attribution des structures 6a, 7 et 8 aux Cthers est baste sur leur transformation a l'aide du tttrc~xyde de ruthenium en lactones correspondantes, 10, 11 et 12.[ IIn connection with work on carbonium ion rearrangements in the tetracyclic diterpenoid field, we have been exploring routes to 13-substituted atisiranes and 12-substituted kauranes and 1 beyeranes. An additional incentive for these I studies has been the discovery of a wide range of 1 natural products with ring C functionality. Compounds of this type include alkaloids derived 1 ' from atisirene (1-4) and rearranged atisirenes (aconitine) (5), kaurenes (6-9) and modified kauranes (1 0,ll) (including gibberellins (1 2,13) and alkaloids (1416)), and beyeranes (17). No synthetic approaches to such systems have been reported apart from that of Coates and Bertram (18) for the beyerane type. The present paper deals with the introduction of substituents into ring C of kauranes and phyllocladanes. In subsequent papers, routes to analogously substituted atisanes and beyeranes will be described.The considerable synthetic utility of the hypoiodite reaction of alcohols, which usually results in attack at a 8-carbon atom, has been reviewed (19). We have now applied this reaction to the ent-kauranols l a and 6, and to the phyllocladanol 2, in which the endo carbinol functions are ideally situated for intramolecular attack on ring C. Since ent-kauren-19-oic acid 'To whom correspondence should be addressed.(13a), accompanied by trachylobanic acid, is readily obtainable from the common sunflower (20), our first experiments were carried out using the kauranol ester 16, which was prepared by hydroboration-oxidation of methyl ent-kauren-19-oate (136). ResultsA mixture of ester 16, 1 g-equiv. of iodine, excess lead te...

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“…New manufacturing routes of GBL are based on the two-stage hydrogenation of economically attractive raw materials such as dimethyl maleate [8] or maleic anhydride [9][10][11]. Tetrahydrofurane can also be used as a precursor to synthesize GBL following a single oxidation step [12].…”

Section: Introductionmentioning

confidence: 99%