Oxidative cleavage sodium periodate

Preparative Methods prepared in two steps from commercially available L-gulonolactone via ketalization and oxidative cleavage with sodium periodate at pH 5.5. Also obtained from l-ascorbic acid via (i) ketalization, reduction (lithium aluminum hydride) and oxidative cleavage (sodium periodate), or (ii) ketalization and oxidative fragmentation using hydrogen peroxide and hypochlorous acid. ... 

Glycol cleavage by oxidation with sodium periodate, lead tetraacetate, or sodium bismuthate, is a useful method for determination of the ring size of glycosides as well as for the assignment of anomeric configuration and position of substituents on the ring. (See Chapters VI and I.)... 

Alicyclic hydroxamic acids undergo several specific oxidative cleavage reactions which may be of diagnostic or preparative value. In the pyrrolidine series compounds of type 66 have been oxidized with sodium hypobromite or with periodates to give y-nitroso acids (113). Ozonolysis gives the corresponding y-nitro acids. The related cyclic aldonitrone.s are also oxidized by periodate to nitroso acids, presumably via the hydroxamic acids.This periodate fission was used in the complex degradation of J -nitrones derived from aconitine. 

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). 

Oxidative cleavage of alkenes using sodium periodate proceeds effectively in a monophasic solution of acetic acid, water, and THF with very low osmium content or osmium-free. The orders of reactivity of alkenes are as follows monosubstituted trisubstituted >1,2 disub-stituted > 1,1-disubstituted > tetrasubstituted alkynes.100 Cleavage with polymer-supported OSO4 catalyst combined with NaI04 allows the reuse of the catalyst.101... 

The oxidative cleavage of v/c-diols to give two carbonyl functions (Eq. 5.3) by periodates was first observed by Malaprade and has since been widely applied to the carbohydrate area.50 Since both the reagent sodium periodate and the carbohydrate substrate are water soluble, the reaction is usually carried out in aqueous media.51 The reaction has been applied to polysaccharides such as starch.52 The periodate oxidations of sodium alginate in water as well as a dispersion in 1 1 ethanol-water mixture have been compared.53 Because sodium alginate forms a highly viscous solution, the oxidation was observed to be more extensive in ethanol-water. 

Oxidation of polysaccharides using 10 mM or greater concentrations of sodium periodate at room temperature results in the cleavage of adjacent hydroxyl-containing carbon-carbon bonds on other sugars besides just sialic acid residues (Lotan et al., 1975). High concentrations... 

Reaction of nitromethane and monosaccharide-derived dialdehydes is a useful tool that has been broadly used for the preparation of nitro and amino sugars, and carbocycles.30 Dialdehydes can easily be obtained by oxidative cleavage of conveniently protected monosaccharides with sodium periodate. Their subsequent Henry reaction with a nitroalkene, commonly nitromethane, usually gives isomeric mixtures that require the isolation of the major isomer.31 Thus, treatment of the D-ribose derivative 27 with sodium periodate gave dialdehyde 28, which was subjected to a Henry reaction with nitromethane, to afford nitrosugar 29 as an epimeric mixture (Scheme 11).32... 

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. 

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). 

Aldehydes and ketones often can be prepared by oxidation of alkenes to 1,2-diols (Sections 11-7C and 11-7D), followed by oxidative cleavage of the 1,2-diols with lead tetraethanoate or sodium periodate. For example,... 

Exercise 16-37 An elegant modification of the two-step procedure to prepare ketones from alkenes by hydroxylation and oxidative cleavage of the diol formed uses a small amount of potassium permanganate (or osmium tetroxide, 0s04) as the catalyst and sodium periodate as the oxidizing agent ... 

Exercise 16-38 Write mechanisms for the oxidative cleavage of 1,2-diols by lead tetraethanoate and sodium periodate based on consideration of the mechanism of chromic acid oxidation (Section 15-6B). ... 

In a first step, the TBS ether is subjected to acid cleavage with copper sulfate in acetone containing a catalytic amount of glacial acetic acid. The resulting diol is then protected as an acetunide. Next, the double bond is oxidatively cleaved with sodium periodate and a catalytic amount of osmium tetroxide to give aldehyde 5. 

Novel nor-seco baccatin 99 was synthesized in 92% yield through oxidative cleavage of the A ring of 14-OH-DAB (75) with periodic acid via the hydroxy ketone intermediate 100 (Scheme 19). Protection of the 7-hydroxyl of 99 as TES ether followed by reduction of the aldehyde with sodium borohydride yielded nor-seco baccatin alcohol 101 in 80% yield. Nor-seco 13-amino-baccatins 102 and 103 were synthesized from 101 and 99a via the Mitsunobu reaction and reductive amination, respectively, in high yields (Scheme 20). 

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