Sodium periodate-Ruthenium oxide

Ruthenium(IV) oxide-Sodium periodate, 268 Ruthenium tetroxide, 268 Tetrachlorotris [ bis (1,4-diphenylphos-phine)butane]diruthenium, 288 Tetrakis(trifluoroacetate)ruthenium, 289... 

V. M. Parikh and J. K. N. Jones, Oxidation of sugars with ruthenium dioxide-sodium periodate a simple method for the preparation of substituted keto sugars, Can. J. Chem., 43 (1965) 3452-3453 compare R. H. Hall and K. Bischofberger, The preparation of aldonolactones and lactols by oxidation of aldoses with ruthenium(VIII) oxide, Carbohydr. Res., 65 (1978) 139-143. 

Sequential alkylation of the lithium enolate of 897 with methyl iodide and then allyl bromide furnishes dialkylated malate 938 with 96 4 diastereoselectivity. The hydroxyl group is removed via a xanthate ester to give 939, which is then alkylated with 4-bromo-l-butene to give 940 as the major isomer. The mixture is hydrolyzed with base and heated with urea to yield imides 941 and 942 in a 3 1 ratio. After isolation of pure 941 by crystallization, the remaining undesired diastereomer 942 is epimerized to 941 with potassium tert-hutoxide. Oxidation of 941 with ruthenium tetroxide-sodium periodate and esterification of the resulting acids furnishes imide 943. This sequence has produced more than 10 g of 943 in a single run. 

Alternatively, reductive dehydroxylation of 326 with zinc-copper couple followed by N-acetylation and debenzylation with lithium in liquid ammonia affords 328. Ruthenium dioxide-sodium periodate oxidative cleavage of the furyl ring and conversion to the methyl ester with diazomethane affords the (R)-a-amino acid ester 329, which is a fully protected a-epimeric jS-alkoxy-a-amino acid [114]. 

An alternative, but rather expensive, method of isolating pure 3/8-acetoxy-5a-lanosta-8,24-dien-3/3-yl acetate from commercial lanosterol has been described. Oxidation of the lanost-8-enes (12) with ruthenium dioxide-sodium periodate gives the 8,9-seco-8,9-diketones (13) together with lesser amounts of the corresponding 8-ene-7,ll-diketones. Under either acidic or basic conditions the former cyclize to afford the C(14a)-homo-B-norlanost-8-en-14a-ones... 

Overall, ozone compares favorably with other approaches for oxidative alkene cleavage involving Osmium Tetroxide, Potassium Permanganate, Ruthenium(VIII) Oxide, Sodium Periodate, or chromyl carboxylates which are costly, toxic, involve metal wastes, and may require detailed workup procedures. 

Ruthenium tetroxide sodium periodate Double benzylic oxidation 9a-Hydroxy-6-ketosteroids... 

Chloro-2-(3-methyl-4H-1,2,4-triazol-4-yDbenzophenone (Oxidation of 7solution prepared by adding sodium periodate (2 g) to a stirred suspension of ruthenium dioxide (200 mg) in water (35 ml). The mixture became dark. Additional sodium periodate 18 g) was added during the next 15 minutes. The ice-bath was removed and the mixture was stirred for 45 minutes. Additional sodium periodate (4 g) was added and the mixture was stirred at ambient temperature for 18 hours and filtered. The solid was washed with acetone and the combined filtrate was concentrated in vacuo. The residue was suspended in water and extracted with methylene chloride. The extract was dried over anhydrous potassium carbonate and concentrated. The residue was chromatographed on silica... 

Oxidation of diethyl 3,6-hexanooxepin-4,5-dicarboxylate with ruthenium(VIII) oxide, generated from ruthenium(III) chloride and sodium periodate in situ, gives the corresponding hexa-no-bridged furan 1 a with loss of two carbon atoms (see Houben-Weyl, Vol. E6a, p 77).200 201 One of the central methylene groups can be replaced by a carbonyl group to give lb.200... 

Osmium tetroxide used in combination with sodium periodate can also effect alkene cleavage.191 Successful oxidative cleavage of double bonds using ruthenium tetroxide and sodium periodate has also been reported.192 In these procedures the osmium or ruthenium can be used in substoichiometric amounts because the periodate reoxidizes the metal to the tetroxide state. Entries 1 to 4 in Scheme 12.18 are examples of these procedures. Entries 5 and 6 show reactions carried out in the course of multistep syntheses. The reaction in Entry 5 followed a 5-exo radical cyclization and served to excise an extraneous carbon. The reaction in Entry 6 followed introduction of the allyl group by enolate alkylation. The aldehyde group in the product was used to introduce an amino group by reductive alkylation (see Section 5.3.1.2). 

Acyl nitroso compounds (3, Scheme 7.2) contain a nitroso group (-N=0) directly attached to a carbonyl carbon. Oxidation of an N-acyl hydroxylamine derivative provides the most direct method for the preparation of acyl C-nitroso compounds [10]. Treatment of hydroxamic acids, N-hydroxy carbamates or N-hydroxyureas with sodium periodate or tetra-alkyl ammonium periodate salts results in the formation of the corresponding acyl nitroso species (Scheme 7.2) [11-14]. Other oxidants including the Dess-Martin periodinane and both ruthenium (II) and iridium (I) based species efficiently convert N-acyl hydroxylamines to the corresponding acyl nitroso compounds [15-18]. The Swern oxidation also provides a useful alternative procedure for the oxidative preparation of acyl nitroso species [19]. Horseradish peroxidase (HRP) catalyzed oxidation of N-hydroxyurea with hydrogen peroxide forms an acyl nitroso species, which can be trapped with 1, 3-cyclohexanone, giving evidence of the formation of these species with enzymatic oxidants [20]. 

Hall and Bischofberger177 found that, when 2,3 5,6-di-0-isopro-pylidene-D-gulono-1,4-lactone was oxidized with ruthenium(VIII) oxide and an excess of sodium periodate, it gave 2,3 5,6-di-0-isopro-pylidene-D-riho-4-hexulosono-l,4-[(R) or (S)]-lactol. Similar results were observed with 2,3 5,6-di-0-isopropylidene-D-mannono-1,4-lactone and 2,3 5,6-di-O-isopropylidene-D-allono-l,4-lactone. This oxidation presumably proceeds by way of lactone cleavage and oxidation of the free 4-hydroxyl group followed, on acidification by relac-tonization, and formation of the new lactol. 

In 1997, Laux and Krause showed that ruthenium(III) chloride can catalyze the oxidation of allenes 48 to a,a -dihydroxy ketones 49 [17]. They used sodium periodate as a stoichiometric oxidant and obtained the products in moderate to good yields, probably owing to overoxidation (Scheme 17.16). The dihydroxy compound was formed with high diastereomeric excess in one example when a chiral allene was oxidized. 

In conjunction with a ruthenium oxide co-catalyst, sodium periodate has been used as a mild oxidizing agent in the presence of benzyltriethylammonium chloride... 

Ruthenium-promoted oxidation of carbohydrates with sodium periodate... 

Hydrated RuCl, (1.5 g, ca. 6.2 mmol) is stirred with sodium periodate (5.5 g, 26 mmol) in H20 (50 ml) for 12 h. The precipitated ruthenium oxide is added at 0-5°C under an atmosphere of oxygen to aqueous TPA-OH (1M, 5 ml) and aqueous NaOH (0.8 M, 50 ml). Precipitated TPA-Ru04 (87%) is collected and washed well with H20 and dried under vacuum. 

Osmium tetroxide used in combination with sodium periodate can also effect alkene cleavage.135 Successful oxidative cleavage of double bonds using ruthenium tetroxide and sodium periodate has also been reported.136 In these procedures, the osmium or ruthenium can be used in substoichiometric amounts because the periodate reoxidizes the metal to the tetroxide state. Entries 1 4 in Scheme 12.17 are examples of these procedures. 

Exposure of 144 to catalytic quantities of ruthenium tetroxide, generated in situ from ruthenium trichloride and sodium periodate, produces the symmetrical lactones 145 <2000JA9558>. It is proposed that the products form as a result of the ruthenium-catalyzed oxidative cleavage of the a-diketones to produce intermediate glycols (Equation 49). 

Pure homoallylic alcohols are converted into y-amino-p-hydroxy acids by protection as the TBDMS ether or A(0-acetonide followed by degradative oxidation of the terminal alkene using a catalytic amount of ruthenium(III) chloride and sodium periodate (Scheme... 

A highly selective conversion of 1,6-anhydro-4-0-benzyl-2-deoxy-2-fluoro-/ -D-glucopyranose (12) into the corresponding 3-oxo derivative 13 is carried out by rulhcnium(VIII) oxide generated in situ from ruthenium(IV) oxide and sodium periodate.199... 

End and Pfalz have reported that chiral ruthenium-bisamide (26) complex is a useful catalyst for epoxidation of E-olefins with sodium periodate as a terminal oxidant, although enantiose-lectivity is moderate (Scheme 6B.25) [70]. It is noteworthy that tranT-(I-mcthylstyrene is a better substrate than m-P-methylstyrene for this reaction in terms of enantioselectivity. Competitive... 

The use of cyclic sulfates in synthetic applications has been limited in the past because, although cyclic sulfites are easily prepared from diols, a convenient method for oxidation of the cyclic sulfites to cyclic sulfates had not been developed. The experiments of Denmark [70] and of Lowe and co-workers [71 ] with stoichiometric ruthenium tetroxide oxidations and of Brandes and Katzenellenbogen [72a] and Gao and Sharpless [68] with catalytic ruthenium tetroxide and sodium periodate as cooxidant have led to an efficient method for this oxidation step. Examples of the conversion of several diols (67) to cyclic sulfites (68) followed by oxidation to cyclic sulfates (69) are listed in Table 6D.7. The cyclic sulfite/cyclic sulfate sequence has been applied to 1,2-, 1,3-, and 1,4-diols with equal success. Cyclic sulfates, like epoxides, are excellent electrophiles and, as a consequence of their stereoelectronic makeup, are less susceptible to the elimination reactions that usually accompany attack by nucleophiles at a secondary carbon. With the development of convenient methods for their syntheses, the reactions of cyclic sulfates have been explored, Most of the reactions have been nucleophilic displacements with opening of the cyclic sulfate ring. The variety of nucleophiles used in this way is already extensive and includes H [68], [68,73-76], F" [68,72,74], PhCOCT [68,73,74], NOJ [68], SCN [68],... 

Two tandem alkene metathesis-oxidation procedures using Grubb s second-generation ruthenium catalyst resulted in unique functional group transformations. Use of sodium periodate and cerium(III) chloride, in acetonitrile-water, furnished cis-diols. Oxidation with Oxone, in the presence of sodium hydrogencarbonate, yielded a-hydroxy ketones.296 Secondary alcohols are oxidized to ketones by a hydrogen... 

However, regiopure azido 1,2-diol 19 is converted to the corresponding azido carboxylic acid 22 by oxidative glycol cleavage with periodic acid in the presence of catalytic amounts of ruthenium trichloride. Interestingly, the use of sodium periodate instead of periodic acid resulted in a 10-15 % epimerization of the C-5 stereocenter. 

The modern protocol for oxidation of cyclic sulfinimidates 113 to corresponding sulfonamidates 114 includes treatment with sodium periodate and catalytic ruthenium trichloride (Equation 25) < 1999J(P 1) 1421, 1999TL3831, 20000L2595>. Yields are almost quantitative. 

The most widely used method for the preparation of 1,3,2-dioxathiolane. Y-oxides (cyclic sulfites) 65 bearing C-linked substituents is the reaction of the corresponding 1,2-diols with thionyl chloride in presence of pyridine or Et3N (Scheme 18). More reactive 1,3,2-dioxathiolane. Y,.Y-dioxidcs (cyclic sulfates) 66 are usually obtained by oxidation of sulfites 65 with sodium periodate, which is mediated by mthenium tetroxide generated in situ from a catalytic amount of ruthenium trichloride. Numerous derivatives 65 and 66 were obtained via this approach and its modifications for further transformations, mostly as the synthetic equivalents of epoxides <1997AHC89, 2000T7051> (see also Sections 6.05.5 and 6.05.6, and Tables 1-7). 

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