Ruthenium chloride-Sodium periodate

Potassium ruthenate, 259 Ruthenium(III) chloride, 268 Ruthenium (III) chloride-Sodium periodate, 105... 

Ruthcniiim(in) chloride- Sodium periodate (seeabo Ruthenium tetroxide), 106 Ruibcniuin(III) chloride-Tributylphospbinc. t[Pg.469]

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... 

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... 

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... 

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... 

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). 

The chiral octanediol in turn is converted into the corresponding cyclic sulfate by reaction with thionyl chloride and subsequent oxidation with sodium periodate and a catalytic amount of ruthenium(ni) chloride (0.1 mol%) (eq 2). In the final step, 1,2-diphosphinobenzene is lithiated by treatment with n-butyllithium (n-BuLi 2 equiv, 1.6 mol% in hexane) followed by the addition of the (3R,6R)-octane-3,6-diol cyclic sulfate (2 equiv) and a further addition of 2.2 equiv of n-BuLi. (5,5)-Ethyl-DuPHOS is obtained in a yield of over 70% [78% yield was described for the (R,R)-enantiomer by an analogous method ]. In addition to (5,5)-ethyl-DuPHOS, a variety of related bisphospholanes either linked by an ethylene bridge, or bearing other 2,5-alkyl substituents, or with opposite configuration have been prepared by this methodology. ... 

Use of the chiral carbon pool for cyclopentenone preparation is also known. The fungal metabolite terrein [88] was selectively monoacetylated and then reduced with chromous chloride to enone [89]. Acetylation and olefin cleavage with ruthenium tetroxide aiwi sodium periodate led to aldehyde [90], which was readily decarbonylated to [65] (51). An alternative route (52) began with the less common S,S-tartaric acid [91], converted in four steps to diiodide [92]. Dialkylation of methyl methylthiomethyl sulfoxide with [92] gave the cyclopentane derivative [93]. Treatment of [93]... 

Amides containing methylene groups linked to the nitrogen atoms are oxidized to imides by ruthenium tetroxide, which is usually generated in situ from ruthenium dioxide or ruthenium chloride and sodium periodate... 

Overhand, Overkleeft and their collaborators have synthesised a variety of SAAs [39]. The synthesis of Fmoc-protected 6 ( Fig. 2) is illustrated in Scheme 2 [15]. Tri-O-acetyl-D-glu-cal was converted into the SAA precursor 43 in five steps. Formation of the trichloroacetimi-date derivative 44 and a subsequent Overman rearrangement was used to introduce the amino group onto the pyran scaffold giving 45. Hydrogenation of the olefin in 45 was accompanied by cleavage of the silyl ether to afford the primary alcohol which was oxidised with a catalytic amount of ruthenium (III) chloride in the presence of sodium periodate giving 46. Subjection... 

Inc. and ruthenium(III) chloride hydrate (5-101 water) was purchased from Fluka. The more expensive periodic acid can replace sodium periodate ... 

A later optimized synthesis also starts from the 1,4-diols. They are then converted into cyclic sulfates with thionyl chloride on mediation of ruthenium chloride and sodium periodate. The sulfates are transformed with dili-thiumbis(phosphido)ethane into bis(phospho-lano)ethane (BPE) ligands or with dilithium-... 

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